Process for preparing branched polyarylene ethers

ABSTRACT

Disclosed is a process for preparing branched polyarylene ether polymers by (A) providing a reaction mixture comprising (i) a polyfunctional phenol compound of the formula Ar(OH) x  wherein x≧3 and wherein Ar is an aryl moiety or an alkylaryl moiety, provided that when Ar is an alkylaryl moiety at least three of the —OH groups are bonded to an aryl portion thereof, (ii) one or more linear polymers of the formula 
                         
wherein m is 0 or 1, A and B are as defined herein, and n is an integer representing the number of repeat monomer units, and (iii) a carbonate base; and (B) heating the reaction mixture and removing generated water from the reaction mixture, thereby effecting a polymerization reaction.

Cross-reference is hereby made to the following copending applications:

Copending Application U.S. Ser. No. 10/322,110, filed Dec. 17, 2002,entitled “Process for Preparing Substituted Polyarylene Ethers,” withthe named inventor Timothy P. Bender, the disclosure of which is totallyincorporated herein by reference, discloses processes for preparingpolymers of the formula

wherein m is 0 or 1, X is chlorine, bromine, or iodine, and n, e, and fare each, independently of the others, integers wherein e may be 0 and nand f are each at least 1, said process comprising providing a firstreaction mixture which comprises a first solvent, a compound of theformula

wherein Y is a chlorine or fluorine atom, a compound of the formula

and optionally, a compound of the formula

heating the first reaction mixture and removing generated watertherefrom, thereby forming an intermediate polymer of the formula

providing a second reaction mixture which comprises a second solvent,the intermediate polymer, and a N-halosuccinimide, wherein the halogenatom in the N-halosuccinimide is the same as the halogen atom that is X;and heating the second reaction mixture, thereby forming the polymer.

Copending Application U.S. Ser. No. 10/040,850, filed Jan. 9, 2002,entitled “Process for Preparing Polyarylene Ethers,” with the namedinventors Timothy P. Bender, Christine DeVisser, Richard A. Burt, PaulF. Smith, and Marko D. Saban, the disclosure of which is totallyincorporated herein by reference, discloses a process for preparing apolymer of the formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units, said process comprising (A) providing areaction mixture which comprises (i) a solvent, (ii) a compound of theformula

(iii) a compound of the formula

(iv) a compound of the formula

wherein a is an integer of from 1 to 5, R′ is a hydrogen atom, an alkylgroup, an aryl group, an arylalkyl group, an alkylaryl group, an alkoxygroup, an aryloxy group, an arylalkyloxy group, an alkylaryloxy group, apolyalkyleneoxy group, or a mixture thereof, and (v) a carbonate base;and (B) heating the reaction mixture and removing generated water fromthe reaction mixture, thereby effecting a polymerization reaction.

Copending Application U.S. Ser. No. 10/036,469, filed Jan. 7, 2002,entitled “High Performance Curable Polymers and Processes for thePreparation Thereof,” with the named inventors Ram S. Narang and TimothyJ. Fuller, the disclosure of which is totally incorporated herein byreference, discloses a composition which comprises a polymer containingat least some monomer repeat units with photosensitivity-impartingsubstituents which enable crosslinking or chain extension of the polymerupon exposure to actinic radiation, said polymer being of the formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units, wherein said photosensitivity-impartingsubstituents are allyl ether groups, epoxy groups, or mixtures thereof.Also disclosed are a process for preparing a thermal ink jet printheadcontaining the aforementioned polymers and processes for preparing theaforementioned polymers.

Copending Application U.S. Ser. No. 10/717,295, filed Nov. 19, 2003,entitled “Unsaturated Ester Substituted Polymers with Reduced HalogenContent,” with the named inventors Christine J. DeVisser and Timothy P.Bender, the disclosure of which is totally incorporated herein byreference, discloses polymers of The formula

wherein x is 0 or 1, R₁₋₄ are alkyl, aryl, arylalkyl, or alkylarylgroups, X₁₋₄ are halogens, a′, b′, c′, and d′ are 0–4, UE is onunsaturated ester group, e, f, g, and h are 0–4, at least one of e, f,g, and h is ≧1 in at least some monomers, SE is a saturated ester group,i, j, k, and m are 0–4 at least one of i, j, k, and m is ≧1 in at leastsome monomers, a′+e+i≦4, b′+f+j≦4, c′+g+k≦4, d′+h+m≦4, RX represents thetotal number of haloalkyl groups in the polymer, the ratio of UE groupsto SE groups to RX groups in the polymer isυε:σε:ρχwherein υε is from about 1 to about 99.99, wherein σε is from about 0.01to about 99, wherein ρχ is from 0 to about 50, and wherein υε+σε+ρχ=100.

Copending Application U.S. Ser. No. 10/721,140, filed concurrentlyherewith, entitled “Branched Polyarylene Ethers and Processes for thePreparation Thereof,” with the named inventor Timothy P. Bender, thedisclosure of which is totally incorporated herein by reference,discloses a process for preparing branched polyarylene ether polymers by(A) providing a reaction mixture comprising (i) a polyfunctional phenolcompound of the formula Ar(OH)_(x) wherein x≧3 and wherein Ar is an arylmoiety or an alkylaryl moiety, provided that when Ar is an alkylarylmoiety at least three of the —OH groups are bonded to an aryl portionthereof, (ii) a compound of the formula

wherein m is 0 or 1, Y and Y′ each, independently of the other, isfluorine or chlorine, and A is as defined therein, (iii) a compound ofthe formula

wherein B is as defined therein, and (iv) a carbonate base; and (B)heating the reaction mixture and removing generated water from thereaction mixture, thereby effecting a polymerization reaction. Alsodisclosed are polymers prepared by this process and imaging memberscontaining these polymers.

BACKGROUND

Disclosed herein are branched polyarylene ether polymers and processesfor preparing these polymers. More specifically, disclosed herein aremethods for preparing branched polyarylene polymers by depolymerizationof linear polyarylene ether polymers. One embodiment disclosed herein isdirected to a process for preparing a branched polyarylene ether polymerwhich comprises (A) providing a reaction mixture which comprises (i) anoptional solvent, (ii) a polyfunctional phenol compound of the formulaAr(OH)_(x) wherein x≧3 and wherein Ar is an aryl moiety or an alkylarylmoiety, provided that

when Ar is an alkylaryl moiety at least three of the —OH groups arebonded to an aryl portion thereof, (iii) one or more linear polymers ofthe formula

wherein each m, independently of the others, is an integer of 0 or 1,each A, independently of the others, is

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R_(x) is an alkylene group, an arylene group, an arylalkylenegroup, an alkylarylene group, or mixtures thereof,

or mixtures thereof, each B, independently of the others, is

wherein z is an integer of from 2 to about 20,

wherein u is an integer of from 1 to about 20,

wherein w is an integer of from 1 to about 20,

wherein each o, independently of the other, is an integer of 1, 2, 3, or4,

wherein R₁ and R₂ each, independently of the other, are hydrogen atoms,alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, ormixtures thereof, and p is an integer of 0 or 1,

wherein b is an integer of 0 or 1,

wherein (1) Z is

wherein c is 0 or 1; (2) Ar′ is

(3) G is an alkyl group selected from alkyl groups containing from about2 to about 10 carbon atoms; (4) Ar″ is

wherein s is 0, 1, or 2,

and (6) q is 0 or 1; or mixtures thereof, and n is an integerrepresenting the number of repeat monomer units, (iv) optionally, acompound of the formula

wherein a is an integer of from 1 to 5 and R′ is a hydrogen atom, analkyl group, an aryl group, an arylalkyl group, an alkylaryl group, or amixture thereof, wherein two or more R′ groups can be joined together toform a ring, and (v) a carbonate base; and (B) heating the reactionmixture and removing generated water from the reaction mixture, therebyeffecting a polymerization reaction.

In microelectronics applications, there is a great need for lowdielectric constant, high glass transition temperature, thermallystable, photopatternable polymers for use as interlayer dielectriclayers and as passivation layers which protect microelectroniccircuitry. Poly(imides) are widely used to satisfy these needs; thesematerials, however, have disadvantageous characteristics such asrelatively high water sorption and hydrolytic instability. There is thusa need for high performance polymers which can be effectivelyphotopatterned and developed at high resolution.

Polyarylene ethers are known polymers for use as high performanceengineering thermoplastics. They exhibit outstanding physical propertiesand high chemical resistance. The use of these materials as photoresistswhen substituted with photoactive substituents is also known. Thesematerials are suitable for use in applications such as thermal ink jetprintheads, other microelectronics applications, printed circuit boards,lithographic printing processes, interlayer dielectrics, and the like.

The formation and development of images on the surface ofphotoconductive materials by electrostatic means is well known. Thebasic electrophotographic imaging process, as taught by C. F. Carlson inU.S. Pat. No. 2,297,691, entails placing a uniform electrostatic chargeon a photoconductive imaging member, exposing the imaging member to alight and shadow image to dissipate the charge on the areas of theimaging member exposed to the light, and developing the resultingelectrostatic latent image by depositing on the image a finely dividedelectroscopic material known as toner. In charge area development (CAD)systems, the toner will normally be attracted to those areas of theimaging member which retain a charge, thereby forming a toner imagecorresponding to the electrostatic latent image. In discharge areadevelopment (DAD) systems, the toner will normally be attracted to thoseareas of the imaging member which have less or no charge as a result ofexposure to light, thereby forming a toner image corresponding to theelectrostatic latent image. This developed image may then be transferredto a substrate such as paper. The transferred image may subsequently bepermanently affixed to the substrate by heat, pressure, a combination ofheat and pressure, or other suitable fixing means such as solvent orovercoating treatment.

Imaging members for electrophotographic imaging systems comprisingselenium alloys vacuum deposited on substrates are known. Imagingmembers have also been prepared by coating substrates withphotoconductive particles dispersed in an organic film forming binder.Coating of rigid drum substrates has been effected by various techniquessuch as spraying, dip coating, vacuum evaporation, and the like.Flexible imaging members can also be manufactured by processes thatentail coating a flexible substrate with the desired photoconductingmaterial.

Some photoresponsive imaging members consist of a homogeneous layer of asingle material such as vitreous selenium, and others comprise compositelayered devices containing a dispersion of a photoconductivecomposition. An example of a composite xerographic photoconductivemember is described in U.S. Pat. No. 3,121,006, which discloses finelydivided particles of a photoconductive inorganic compound dispersed inan electrically insulating organic resin binder. Imaging membersprepared according to the teachings of this patent contain a binderlayer with particles of zinc oxide uniformly dispersed therein coated ona paper backing. The binders disclosed in this patent include materialssuch as polycarbonate resins, polyester resins, polyamide resins, andthe like.

Photoreceptor materials comprising inorganic or organic materialswherein the charge generating and charge transport functions areperformed by discrete contiguous layers are also known. Additionally,layered photoreceptor members are disclosed in the prior art, includingphotoreceptors having an overcoat layer of an electrically insulatingpolymeric material. Other layered photoresponsive devices have beendisclosed, including those comprising separate photogenerating layersand charge transport layers as described in U.S. Pat. No. 4,265,990, thedisclosure of which is totally incorporated herein by reference.Photoresponsive materials containing a hole injecting layer overcoatedwith a hole transport layer, followed by an overcoating of aphotogenerating layer, and a top coating of an insulating organic resin,are disclosed in U.S. Pat. No. 4,251,612, the disclosure of which istotally incorporated herein by reference. Examples of photogeneratinglayers disclosed in these patents include trigonal selenium andphthalocyanines, while examples of transport layers include certain aryldiamines as illustrated therein.

In addition, U.S. Pat. No. 3,041,167 discloses an overcoated imagingmember containing a conductive substrate, a photoconductive layer, andan overcoating layer of an electrically insulating polymeric material.This member can be employed in electrophotographic imaging processes byinitially charging the member with an electrostatic charge of a firstpolarity, followed by exposing it to form an electrostatic latent imagethat can subsequently be developed to form a visible image.

U.S. Pat. No. 5,994,425 (Narang et al.), U.S. Pat. No. 6,022,095 (Naranget al.), EP 827027, and JP 10120743, the disclosures of each of whichare totally incorporated herein by reference, disclose an improvedcomposition comprising a photopatternable polymer containing at leastsome monomer repeat units with photosensitivity-imparting substituents,said photopatternable polymer being of the general formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units. Also disclosed is a process for preparing athermal ink jet printhead with the aforementioned polymer and a thermalink jet printhead containing therein a layer of a crosslinked or chainextended polymer of the above formula.

U.S. Pat. No. 5,849,809 (Narang et al.), U.S. Pat. No. 6,203,143 (Naranget al.), EP 827028, and JP 10090895, the disclosures of each of whichare totally incorporated herein by reference, disclose a compositionwhich comprises (a) a polymer containing at least some monomer repeatunits with photosensitivity-imparting substituents which enablecrosslinking or chain extension of the polymer upon exposure to actinicradiation, said polymer being of the formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units, wherein said photosensitivity-impartingsubstituents are hydroxyalkyl groups; (b) at least one member selectedfrom the group consisting of photoinitiators and sensitizers; and (c) anoptional solvent. Also disclosed are processes for preparing the abovepolymers and methods of preparing thermal ink jet printheads containingthe above polymers.

U.S. Pat. No. 6,124,372 (Smith et al.), U.S. Pat. No. 6,151,042 (Smithet al.), U.S. Pat. No. 6,323,301 (Smith et al.), EP 827029, and JP10097073, the disclosures of each of which are totally incorporatedherein by reference, disclose a composition comprising a polymer with aweight average molecular weight of from about 1,000 to about 100,000,said polymer containing at least some monomer repeat units with a first,photosensitivity-imparting substituent which enables crosslinking orchain extension of the polymer upon exposure to actinic radiation, saidpolymer also containing a second, thermal sensitivity-impartingsubstituent which enables further crosslinking or chain extension of thepolymer upon exposure to temperatures of about 140° C. and higher,wherein the first substituent is not the same as the second substituent,said polymer being selected from the group consisting of polysulfones,polyphenylenes, polyether sulfones, polyimides, polyamide imides,polyarylene ethers, polyphenylene sulfides, polyarylene ether ketones,phenoxy resins, polycarbonates, polyether imides, polyquinoxalines,polyquinolines, polybenzimidazoles, polybenzoxazoles,polybenzothiazoles, polyoxadiazoles, copolymers thereof, and mixturesthereof.

U.S. Pat. No. 5,889,077 (Fuller et al.), U.S. Pat. No. 6,087,414 (Fulleret al.), EP 827030, and JP 10090894, the disclosures of each of whichare totally incorporated herein by reference, disclose a process whichcomprises reacting a polymer of the general formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units, with (i) a formaldehyde source, and (ii) anunsaturated acid in the presence of an acid catalyst, thereby forming acurable polymer with unsaturated ester groups. Also disclosed is aprocess for preparing an ink jet printhead with the above polymer.

U.S. Pat. No. 5,739,254 (Fuller et al.), U.S. Pat. No. 5,753,783 (Fulleret al.), EP 826700, and JP 10087817, the disclosures of each of whichare totally incorporated herein by reference, disclose a process whichcomprises reacting a polymer of the general formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units, with an acetyl halide and dimethoxymethane inthe presence of a halogen-containing Lewis acid catalyst and methanol,thereby forming a haloalkylated polymer. In a specific embodiment, thehaloalkylated polymer is then reacted further to replace at least someof the haloalkyl groups with photosensitivity-imparting groups. Alsodisclosed is a process for preparing a thermal ink jet printhead withthe aforementioned polymer.

U.S. Pat. No. 5,761,809 (Fuller et al.), EP 827026, and JP 10090896, thedisclosures of each of which are totally incorporated herein byreference, disclose a process which comprises reacting a haloalkylatedaromatic polymer with a material selected from the group consisting ofunsaturated ester salts, alkoxide salts, alkylcarboxylate salts, andmixtures thereof, thereby forming a curable polymer having functionalgroups corresponding to the selected salt. Another embodiment isdirected to a process for preparing an ink jet printhead with thecurable polymer thus prepared.

U.S. Pat. No. 5,958,995 (Narang et al.), U.S. Pat. No. 6,184,263 (Naranget al.), EP 827031, and JP 10104836, the disclosures of each of whichare totally incorporated herein by reference, disclose a compositionwhich comprises a mixture of (A) a first component comprising a polymer,at least some of the monomer repeat units of which have at least onephotosensitivity-imparting group thereon, said polymer having a firstdegree of photosensitivity-imparting group substitution measured inmilliequivalents of photosensitivity-imparting group per gram and beingof the general formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units, and (B) a second component which compriseseither (1) a polymer having a second degree ofphotosensitivity-imparting group substitution measured inmilliequivalents of photosensitivity-imparting group per gram lower thanthe first degree of photosensitivity-imparting group substitution,wherein said second degree of photosensitivity-imparting groupsubstitution may be zero, wherein the mixture of the first component andthe second component has a third degree of photosensitivity-impartinggroup substitution measured in milliequivalents ofphotosensitivity-imparting group per gram which is lower than the firstdegree of photosensitivity-imparting group substitution and higher thanthe second degree of photosensitivity-imparting group substitution, or(2) a reactive diluent having at least one photosensitivity-impartinggroup per molecule and having a fourth degree ofphotosensitivity-imparting group substitution measured inmilliequivalents of photosensitivity-imparting group per gram, whereinthe mixture of the first component and the second component has a fifthdegree of photosensitivity-imparting group substitution measured inmilliequivalents of photosensitivity-imparting group per gram which ishigher than the first degree of photosensitivity-imparting groupsubstitution and lower than the fourth degree ofphotosensitivity-imparting group substitution; wherein the weightaverage molecular weight of the mixture is from about 10,000 to about.50,000; and wherein the third or fifth degree ofphotosensitivity-imparting group substitution is from about 0.25 toabout 2 milliequivalents of photosensitivity-imparting groups per gramof mixture. Also disclosed is a process for preparing a thermal ink jetprinthead with the aforementioned composition.

U.S. Pat. No. 5,945,253 (Narang et al.), U.S. Pat. No. 6,365,323 (Naranget al.), EP 827033, and JP 10090897, the disclosures of each of whichare totally incorporated herein by reference, disclose a compositionwhich comprises a polymer containing at least some monomer repeat unitswith photosensitivity-imparting substituents which enable crosslinkingor chain extension of the polymer upon exposure to actinic radiation,said polymer being of the formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units, wherein said photosensitivity-impartingsubstituents are allyl ether groups, epoxy groups, or mixtures thereof.Also disclosed are a process for preparing a thermal ink jet printheadcontaining the aforementioned polymers and processes for preparing theaforementioned polymers.

U.S. Pat. No. 5,863,963 (Narang et al.), U.S. Pat. No. 6,090,453 (Naranget al.), and JP 10090899, the disclosures of each of which are totallyincorporated herein by reference, disclose a process which comprises thesteps of (a) providing a polymer containing at least some monomer repeatunits with halomethyl group substituents which enable crosslinking orchain extension of the polymer upon exposure to a radiation source whichis electron beam radiation, x-ray radiation, or deep ultravioletradiation, said polymer being of the formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units, and (b) causing the polymer to becomecrosslinked or chain extended through the photosensitivity-impartinggroups. Also disclosed is a process for preparing a thermal ink jetprinthead by the aforementioned curing process.

U.S. Pat. No. 6,007,877 (Narang et al.), U.S. Pat. No. 6,273,543 (Naranget al.), EP 827032, and JP 10090898, the disclosures of each of whichare totally incorporated herein by reference, disclose a compositionwhich comprises a polymer containing at least some monomer repeat unitswith water-solubility- or water-dispersability-imparting substituentsand at least some monomer repeat units with photosensitivity-impartingsubstituents which enable crosslinking or chain extension of the polymerupon exposure to actinic radiation, said polymer being of the formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units. In one embodiment, a single functional groupimparts both photosensitivity and water solubility or dispersability tothe polymer. In another embodiment, a first functional group impartsphotosensitivity to the polymer and a second functional group impartswater solubility or dispersability to the polymer. Also disclosed is aprocess for preparing a thermal ink jet printhead with theaforementioned polymers.

U.S. Pat. No. 5,814,426 (Fuller et al.), EP 918257, and JP 11218943, thedisclosures of each of which are totally incorporated herein byreference, disclose an imaging member which comprises a conductivesubstrate, a photogenerating material, and a binder which comprises apolymer of the formulae I, II, III, IV, V, VI, VII, VIII, IX, or X asfurther defined therein.

U.S. Pat. No. 5,882,814 (Fuller et al.), EP 918256, and JP 11223956, thedisclosures of each of which are totally incorporated herein byreference, disclose an imaging member which comprises a conductivesubstrate, a photogenerating layer, and a charge transport layercomprising a polymer of the formulae I, II, III, IV, V, VI, VII, VIII,IX, or X as further defined therein.

U.S. Pat. No. 5,874,192 (Fuller et al.), EP 918258, and JP 11223955, thedisclosures of each of which are totally incorporated herein byreference, disclose an imaging member which comprises a conductivesubstrate, a photogenerating material, a charge transport material, anda polymeric binder comprising (a) a first polymer comprising apolycarbonate, and (b) a second polymer of the formulae I, II, III, IV,V, VI, VII, VIII, IX, or X as further defined therein.

U.S. Pat. No. 6,273,985 (DeLouise et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forbonding a first article to a second article which comprises (a)providing a first article comprising a polymer havingphotosensitivity-imparting substituents; (b) providing a second articlecomprising metal, plasma nitride, silicon, or glass; (c) applying to atleast one of the first article and the second article an adhesionpromoter selected from silanes, titanates, or zirconates having (i)alkoxy, aryloxy, or arylalkyloxy functional groups and (ii) functionalgroups including at least one photosensitive aliphatic >C═C< linkage;(d) placing the first article in contact with the second article; and(e) exposing the first article, second article, and adhesion promoter toradiation, thereby bonding the first article to the second article withthe adhesion promoters. In one embodiment, the adhesion promoter isemployed in microelectrical mechanical systems such as thermal ink jetprintheads.

U.S. Pat. No. 6,260,956 (Narang et al.), the disclosure of which istotally incorporated herein by reference, discloses an ink jet printheadwhich comprises (i) an upper substrate with a set of parallel groovesfor subsequent use as ink channels and a recess for subsequent use as amanifold, the grooves being open at one end for serving as dropletemitting nozzles, and (ii) a lower substrate in which one surfacethereof has an array of heating elements and addressing electrodesformed thereon, said lower substrate having an insulative layerdeposited on the surface thereof and over the heating elements andaddressing electrodes and patterned to form recesses therethrough toexpose the heating elements and terminal ends of the addressingelectrodes, the upper and lower substrates being aligned, mated, andbonded together to form the printhead with the grooves in the uppersubstrate being aligned with the heating elements in the lower substrateto form droplet emitting nozzles, said upper substrate comprising amaterial formed by crosslinking or chain extending a polymer of formulaI or II.

U.S. Pat. No. 6,117,967 (Fuller et al.) and JP 200119761, thedisclosures of each of which are totally incorporated herein byreference, discloses a polymer of the formula

wherein A is

or a mixture of

wherein R is a hydrogen atom, an alkyl group, an aryl group, or mixturesthereof, B is one of specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units.

U.S. Pat. No. 6,177,238 (Fuller et al.), the disclosure of which istotally incorporated herein by reference, discloses an ink jet printheadcontaining a polymer of the formula

wherein P is a substituent which enables crosslinking of the polymer, a,b, c, and d are each integers of 0, 1, 2, 3, or 4, provided that atleast one of a, b, c, and d is equal to or greater than 1 in at leastsome of the monomer repeat units of the polymer, A is

or a mixture of

wherein R is a hydrogen atom, an alkyl group, an aryl group, or mixturesthereof, B is one of specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units.

U.S. Pat. No. 6,174,636 (Fuller et al.), the disclosure of which istotally incorporated herein by reference, discloses an imaging memberwhich comprises a conductive substrate, a photogenerating material, anda binder comprising a polymer of the formula

wherein A is

or a mixture of

wherein R is a hydrogen atom, an alkyl group, an aryl group, or mixturesthereof, B is one of specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units.

U.S. Pat. No. 6,187,512 (Foucher et al.) and JP 2000344884, thedisclosures of each of which are totally incorporated herein byreference, disclose a process which comprises reacting a polymer of thegeneral formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units, with a halomethyl alkyl ether, an acetylhalide, and methanol in the presence of a halogen-containing Lewis acidcatalyst, thereby forming a halomethylated polymer.

U.S. Pat. No. 6,020,119 (Foucher et al.), the disclosure of which istotally incorporated herein by reference, discloses a process whichcomprises reacting a polymer of the general formula

wherein x is an integer of 0 or 1, A is one of several specified groups,such as

B is one of several specified groups, such as

or mixtures thereof, and n is an integer representing the number ofrepeating monomer units, with a halomethylethyl ether, a hydrohalicacid, and acetic acid in the presence of a halogen-containing Lewis acidcatalyst, thereby forming a halomethylated polymer.

U.S. Pat. No. 6,139,920 (Smith et al.) and U.S. Pat. No. 6,260,949(Smith et al.), the disclosures of each of which are totallyincorporated herein by reference, disclose a composition comprising ablend of (a) a thermally reactive polymer selected from the groupconsisting of resoles, novolacs, thermally reactive polyarylene ethers,and mixtures thereof; and (b) a photoreactive epoxy resin that isphotoreactive in the absence of a photocationic initiator.

U.S. Pat. No. 5,773,553 (Fuller et al.) and U.S. Pat. No. 5,869,595(Fuller et al.), the disclosures of each of which are totallyincorporated herein by reference, disclose a process which comprisesreacting a polyimide precursor with borane. Also disclosed is a thermalink jet printhead containing a layer comprising the product of thisreaction.

U.S. Pat. No. 5,939,206 (Kneezel et al.) and JP 10100410, thedisclosures of each of which are totally incorporated herein byreference, disclose an apparatus which comprises at least onesemiconductor chip mounted on a substrate, said substrate comprising aporous, electrically conductive member having electrophoreticallydeposited thereon a coating of a polymeric material. In one embodiment,the semiconductor chips are thermal ink jet printhead subunits.

U.S. Pat. No. 6,485,130 (DeLouise et al.), the disclosure of which istotally incorporated herein by reference, discloses a process forbonding a first article to a second article which comprises (a)providing a first article comprising a polymer havingphotosensitivity-imparting substituents; (b) providing a second articlecomprising metal, plasma nitride, silicon, or glass; (c) applying to atleast one of the first article and the second article an adhesionpromoter selected from silanes, titanates, or zirconates having (i)alkoxy, aryloxy, or arylalkyloxy functional groups and (ii) functionalgroups including at least one photosensitive aliphatic >C═C< linkage;(d) placing the first article in contact with the second article; and(e) exposing the first article, second article, and adhesion promoter toradiation, thereby bonding the first article to the second article withthe adhesion promoter. In one embodiment, the adhesion promoter isemployed in microelectrical mechanical systems such as thermal ink jetprintheads.

“Cyclodepolymerisation of bisphenol A polysulfone: evidence forself-complementarity in macrocyclic poly(ether sulfones),” Ian Baxter etal., Chem. Commun., 1998, page 2213, the disclosure of which is totallyincorporated herein by reference, discloses bisphenol A polysulfoneundergoing fluoride-promoted cyclodepolymerisation; high molar masspolymer was thus transformed into a series of macrocyclic oligomerscontaining up to at least 72 aromatic rings; those containing up to 24rings were isolated as pure compounds, and single-crystal X-ray studiesof the cyclotrimer and cyclotetramer revealed shape-complementary pairsand chains of macrocyles, respectively.

“Hyperbranched Polymers 10 Years After,” Y. H. Kim, Journal of PolymerScience: Part A: Polymer Chemistry, Vol. 36, 1685–1698 (1998), thedisclosure of which is totally incorporated herein by reference,discloses that hyperbranched polymers, as well as dendrimers, may findutilities in the areas where the structural uniqueness of these polymersgives merit. There has been much progress in the structuralunderstanding and the methods of synthesis of these polymers. However,functional understanding and utility of these polymers are still ininfancy. Better understanding on physical properties of these polymers,such as solubility and miscibility of these polymers in solvents or withpolymers, and functional group dependency to the thermal relaxationprocess are needed for further development of the subject.

“Randomly Branched Bisphenol A Polycarbonates. I. Molecular WeightDistribution Modeling, Interfacial Synthesis, and Characterization,” M.J. Marks et al., Journal of Polymer Science: Part A: Polymer Chemistry,Vol. 38, 560–570 (2000), the disclosure of which is totally incorporatedherein by reference, discloses that randomly branched bisphenol Apolycarbonates (PCs) were prepared by interfacial polymerization methodsto explore the limits of gel-free compositions available by theadjustment of various composition and process variables. A molecularweight distribution (MWD) model was devised to predict the MWD, G, andweight-average molecular weight per arm (M_(w)/arm) values based on thecomposition variables. The amounts of the monomer, branching agent, andchain terminator were adjusted such that the weight-averagefunctionality of the phenolic monomers (FOH) was less than 2 to precludegel formation in both the long- and short-chain branched (SCB) PCs.Several series of SCB and long-chain branched PCs were prepared, andthose lacking gels showed molecular weights measured by gel permeationchromatography-UV and gel permeation chromatography-LS consistent withmodel calculations. In SCB PCs, the minimum M_(w)/arm that could berealized without gel formation depended on both composition (molecularweight, terminator type) and process (terminator addition point,coupling catalyst) variables. The minimum M_(w)/arm achieved in the lowmolecular weight series studied ranged from ˜3300 to ˜1000. The use oflong chain alkyl phenol terminators gave branched PCs with lowerglass-transition temperatures but a higher gel-free minimum M_(w)/arm.SCB PCs where M_(w)/arm was less than ˜M_(c) spontaneously cracked aftercompression molding, a result attributed to their lack of polymer chainentanglements.

“Hyperbranched poly(arylene ether phosphine oxide)s,” H. S. Lee et al.,Polymer Bulletin, 45, 319–326 (2000), the disclosure of which is totallyincorporated herein by reference, discloses that new AB₂ and A₂Bmonomers, bis(4-fluorophenyl)-4′-hydroxyphenylphosphine oxide andbis(4-hydroxyphenyl)-4′-fluorophenyl-phosphine oxide, were prepared andconverted to corresponding hyperbranched poly(arylene etherphosphineoxide)s with hydroxyphenyl and fluorophenyl end functionalgroups. While the dihydroxy monomer gave a low molecular weight polymer,the difluoro monomer produced a high molecular weight hyperbranchedpolymer. The glass transition temperature of the obtained polymers was266° C. and 230° C., and 5% weight loss temperature was 491° C. and 391°C., respectively. The fluorophenyl-terminated hyperbranched polymer wassoluble in CHCl₃, but the hydroxyphenyl-terminated polymer was notsoluble in CHCl₃ even though it has lower molecular weight than thefluorophenyl-terminated polymer, indicating that properties of thehyperbranched polymers markedly depend on end functional groups as wellas their molecular weight.

Hyperbranched polymers and processes for the preparation thereof areknown. Known syntheses, however, frequently entail the use ofcustom-synthesized monomers, which can take, for example, two to fivesteps to prepare prior to synthesis of the hyperbranched polymer.Accordingly, processes which enable the preparation of branchedpolyarylene ether polymers by simpler processes are desirable.Hyperbranched polymers can have several advantages over linear polymersof the same class. For example, branched polymers (hyperbranches anddendrimers) can exhibit a lower solution and melt viscosities comparedto their linear analogs owing to their lower hydrodynamic volume for thesame molecular weight. In addition, hyperbranched polymers are oftenmore soluble than their linear analogs, which is thought to beattributable to a decrease in the ability of the polymeric material tointertwine at a molecular level. Further, hyperbranched polymers can bethought to be a mid-point between linear polymers and crosslinkedpolymers, since severing of or more of the branches will not result in alarge loss of molecular weight.

Accordingly, while known compositions and processes are suitable fortheir intended purposes, a need remains for branched polyarylene etherpolymers. In addition, a need remains for methods for preparing branchedpolyarylene ether polymers. Further, a need remains for methods forpreparing branched polyarylene ether polymers wherein the synthesis canbe carried out by depolymerization of linear polymers. There is also aneed for methods for preparing branched polyarylene ether polymers thatenables control of the degree of branching within the polymer and theintroduction of branching in a well-defined manner. In addition, thereis a need for methods for preparing branched polyarylene ether polymersthat can be carried out at desirably low cost levels. Further, there isa need for methods for preparing branched polyarylene ether polymerswherein variations in the ratio of monomers can result in control overthe degree of branching and the length of the linear units.Additionally, there is a need for improved photosensitive imagingmembers. A need also remains for improved binders for photosensitiveimaging members. In addition, there is a need for polymeric binderssuitable for use in photogenerating layers in imaging members. Further,a need remains for polymeric binders suitable for use in chargetransport layers in imaging members. Additionally, a need remains forpolymeric binders suitable for use in photosensitive imaging membersthat can, in some embodiments, impart improved wear resistance to themembers, particularly under bias charging roll charging conditions.There is also a need for polymeric binders suitable for use inphotosensitive imaging members that can solubilize charge transportmaterials and other small molecule dopants used to tailor the physicaland/or mechanical properties of the imaging members.

SUMMARY

Disclosed herein is a process for preparing a branched polyarylene etherpolymer which comprises (A) providing a reaction mixture which comprises(i) an optional solvent, (ii) a polyfunctional phenol compound of theformula Ar(OH)_(x) wherein x≧3 and wherein Ar is an aryl moiety or analkylaryl moiety, provided that when Ar is an alkylaryl moiety at leastthree of the —OH groups are bonded to an aryl portion thereof, (iii) oneor more linear polymers of the formula

wherein each m, independently of the others, is an integer of 0 or 1,each A, independently of the others, is

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R_(x) is an alkylene group, an arylene group, an arylalkylenegroup, an alkylarylene group, or mixtures thereof,

or mixtures thereof, each B, independently of the others, is

wherein z is an integer of from 2 to about 20,

wherein u is an integer of from 1 to about 20,

wherein w is an integer of from 1 to about 20,

wherein each o, independently of the other, is an integer of 1, 2, 3, or4,

wherein R₁ and R₂ each, independently of the other, are hydrogen atoms,alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, ormixtures thereof, and p is an integer of 0 or 1,

wherein b is an integer of 0 or 1,

wherein (1) Z is

wherein c is 0 or 1; (2) Ar′ is

(3) G is an alkyl group selected from alkyl groups containing from about2 to about 10 carbon atoms; (4) Ar′ is

wherein s is 0, 1, or 2,

and (6) q is 0 or 1; or mixtures thereof, and n is an integerrepresenting the number of repeat monomer units, (iv) optionally, acompound of the formula

wherein a is an integer of from 1 to 5 and R′ is a hydrogen atom, analkyl group, an aryl group, an arylalkyl group, an alkylaryl group, or amixture thereof, wherein two or more R′ groups can be joined together toform a ring, and (v) a carbonate base; and (B) heating the reactionmixture and removing generated water from the reaction mixture, therebyeffecting a polymerization reaction.

DETAILED DESCRIPTION

Disclosed herein is a process for preparing a branched polyarylene etherpolymer which comprises (A) providing a reaction mixture which comprises(i) an optional solvent, (ii) a polyfunctional phenol compound of theformula Ar(OH)_(x) wherein x≧3 and wherein Ar is an aryl moiety(including substituted and unsubstituted aryl moieties, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the aryl moiety), in oneembodiment with at least about 4 carbon atoms, in another embodimentwith at least about 5 carbon atoms, and in yet another embodiment withat least about 6 carbon atoms, and in one embodiment with no more thanabout 20 carbon atoms, in another embodiment with no more than about 15carbon atoms, and in yet another embodiment with no more than about 10carbon atoms, although the number of carbon atoms can be outside ofthese ranges, or an alkylaryl moiety (including substituted andunsubstituted alkylaryl moieties, and wherein the alkyl portion thereofcan be linear, branched, cyclic, saturated, or unsaturated, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the arylportion and the alkyl portion of the alkylaryl moiety), in oneembodiment with at least about 5 carbon atoms, in another embodimentwith at least about 6 carbon atoms, and in yet another embodiment withat least about 7 carbon atoms, and in one embodiment with no more thanabout 20 carbon atoms, in another embodiment with no more than about 15carbon atoms, and in yet another embodiment with no more than about 9carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as tolyl or the like, wherein the substituents on thesubstituted aryl and alkylaryl groups can be (but are not limited to)hydroxy groups, halogen atoms, amine groups, imine groups, ammoniumgroups, cyano groups, pyridine groups, pyridinium groups, ether groups,aldehyde groups, ketone groups, ester groups, amide groups, carbonylgroups, thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonicacid groups, sulfide groups, sulfoxide groups, phosphine groups,phosphonium groups, phosphate groups, nitrile groups, mercapto groups,nitro groups, nitroso groups, sulfone groups, acyl groups, acidanhydride groups, azide groups, azo groups, cyanato groups, isocyanatogroups, thiocyanato groups, isothiocyanato groups, carboxylate groups,carboxylic acid groups, urethane groups, urea groups, mixtures thereof,and the like, wherein two or more substituents can be joined together toform a ring, provided that when Ar is an alkylaryl moiety at least threeof the —OH groups are bonded to an aryl portion thereof, (iii) one ormore linear polymers of the formula

wherein each m, independently of the others, is an integer of 0 or 1,each A, independently of the others, is

wherein R is a hydrogen atom, an alkyl group (including linear,branched, cyclic, saturated, unsaturated, substituted, and unsubstitutedalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, and the like either may or may not bepresent in the alkyl group), in one embodiment with at least 1 carbonatom, and in one embodiment with no more than about 20 carbon atoms, inanother embodiment with no more than about 10 carbon atoms, and in yetanother embodiment with no more than about 5 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, an aryl group(including substituted and unsubstituted aryl groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and thelike either may or may not be present in the aryl group), in oneembodiment with at least about 4 carbon atoms, in another embodimentwith at least about 5 carbon atoms, and in yet another embodiment withat least about 6 carbon atoms, and in one embodiment with no more thanabout 18 carbon atoms, in another embodiment with no more than about 12carbon atoms, and in yet another embodiment with no more than about 6carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkyl group (including substituted andunsubstituted arylalkyl groups, and wherein the alkyl portion thereofcan be linear, branched, cyclic, saturated, or unsaturated, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the arylportion and the alkyl portion of the arylalkyl group), in one embodimentwith at least about 5 carbon atoms, in another embodiment with at leastabout 6 carbon atoms, and in yet another embodiment with at least about7 carbon atoms, and in one embodiment with no more than about 25 carbonatoms, in another embodiment with no more than about 12 carbon atoms,and in yet another embodiment with no more than about 7 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas benzyl or the like, an alkylaryl group (including substituted andunsubstituted alkylaryl groups, and wherein the alkyl portion thereofcan be linear, branched, cyclic, saturated, or unsaturated, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the arylportion and the alkyl portion of the alkylaryl group), in one embodimentwith at least about 5 carbon atoms, in another embodiment with at leastabout 6 carbon atoms, and in yet another embodiment with at least about7 carbon atoms, and in one embodiment with no more than about 25 carbonatoms, in another embodiment with no more than about 12 carbon atoms,and in yet another embodiment with no more than about 7 carbon atoms,although the number of carbon atoms can be outside of these ranges, suchas tolyl or the like, or mixtures thereof, wherein the substituents onthe substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (butare not limited to) hydroxy groups, halogen atoms, amine groups, iminegroups, ammonium groups, cyano groups, pyridine groups, pyridiniumgroups, ether groups, aldehyde groups, ketone groups, ester groups,amide groups, carbonyl groups, thiocarbonyl groups, sulfate groups,sulfonate groups, sulfonic acid groups, sulfide groups, sulfoxidegroups, phosphine groups, phosphonium groups, phosphate groups, nitrilegroups, mercapto groups, nitro groups, nitroso groups, sulfone groups,acyl groups, acid anhydride groups, azide groups, azo groups, cyanatogroups, isocyanato groups, thiocyanato groups, isothiocyanato groups,carboxylate groups, carboxylic acid groups, urethane groups, ureagroups, mixtures thereof, and the like, wherein two or more substituentscan be joined together to form a ring,

wherein R_(x) is an alkylene group (including linear, branched, cyclic,saturated, unsaturated, substituted, and unsubstituted alkylene groups,and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in thealkylene group), in one embodiment with at least 1 carbon atom, and inone embodiment with no more than about 20 carbon atoms, in anotherembodiment with no more than about 10 carbon atoms, and in yet anotherembodiment with no more than about 5 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an arylene group(including substituted and unsubstituted arylene groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the arylene group), in oneembodiment with at least about 4 carbon atoms, in another embodimentwith at least about 5 carbon atoms, and in yet another embodiment withat least about 6 carbon atoms, and in one embodiment with no more thanabout 18 carbon atoms, in another embodiment with no more than about 12carbon atoms, and in yet another embodiment with no more than about 6carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an arylalkylene group (including substituted andunsubstituted arylalkylene groups, and wherein the alkyl portion thereofcan be linear, branched, cyclic, saturated, or unsaturated, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the arylportion and the alkyl portion of the arylalkylene group), in oneembodiment with at least about 5 carbon atoms, in another embodimentwith at least about 6 carbon atoms, and in yet another embodiment withat least about 7 carbon atoms, and in one embodiment with no more thanabout 25 carbon atoms, in another embodiment with no more than about 12carbon atoms, and in yet another embodiment with no more than about 7carbon atoms, although the number of carbon atoms can be outside ofthese ranges, such as benzylene or the like, an alkylarylene group(including substituted and unsubstituted alkylarylene groups, andwherein the alkyl portion thereof can be linear, branched, cyclic,saturated, or unsaturated, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the aryl portion and the alkylportion of the alkylarylene group), in one embodiment with at leastabout 5 carbon atoms, in another embodiment with at least about 6 carbonatoms, and in yet another embodiment with at least about 7 carbon atoms,and in one embodiment with no more than about 25 carbon atoms, inanother embodiment with no more than about 12 carbon atoms, and in yetanother embodiment with no more than about 7 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as tolyleneor the like, or mixtures thereof, wherein the substituents on thesubstituted alkylene, arylene, arylalkylene, and alkylarylene groups canbe (but are not limited to) hydroxy groups, halogen atoms, amine groups,imine groups, ammonium groups, cyano groups, pyridine groups, pyridiniumgroups, ether groups, aldehyde groups, ketone groups, ester groups,amide groups, carbonyl groups, thiocarbonyl groups, sulfate groups,sulfonate groups, sulfonic acid groups, sulfide groups, sulfoxidegroups, phosphine groups, phosphonium groups, phosphate groups, nitrilegroups, mercapto groups, nitro groups, nitroso groups, sulfone groups,acyl groups, acid anhydride groups, azide groups, azo groups, cyanatogroups, isocyanato groups, thiocyanato groups, isothiocyanato groups,carboxylate groups, carboxylic acid groups, urethane groups, ureagroups, mixtures thereof, and the like, wherein two or more substituentscan be joined together to form a ring,

or mixtures thereof, each B, independently of the others, is

wherein z is an integer of from 2 to about 20,

wherein u is an integer of from 1 to about 20,

wherein w is an integer of from 1 to about 20,

wherein each o, independently of the other, is an integer of 1, 2, 3, or4,

wherein R₁ and R₂ each, independently of the other, are hydrogen atoms,alkyl groups (including linear, branched, cyclic, saturated,unsaturated, substituted, and unsubstituted alkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in the alkyl group), in oneembodiment with at least 1 carbon atom, and in one embodiment with nomore than about 20 carbon atoms, in another embodiment with no more thanabout 10 carbon atoms, and in yet another embodiment with no more thanabout 5 carbon atoms, although the number of carbon atoms can be outsideof these ranges, aryl groups (including substituted and unsubstitutedaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 4 carbon atoms,in another embodiment with at least about 5 carbon atoms, and in yetanother embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 18 carbon atoms, in anotherembodiment with no more than about 12 carbon atoms, and in yet anotherembodiment with no more than about 6 carbon atoms, although the numberof carbon atoms can be outside of these ranges, arylalkyl groups(including substituted and unsubstituted arylalkyl groups, and whereinthe alkyl portion thereof can be linear, branched, cyclic, saturated, orunsaturated, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the aryl portion and the alkyl portion of thearylalkyl group), in one embodiment with at least about 5 carbon atoms,in another embodiment with at least about 6 carbon atoms, and in yetanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 25 carbon atoms, in anotherembodiment with no more than about 12 carbon atoms, and in yet anotherembodiment with no more than about 7 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as benzyl or thelike, alkylaryl groups (including substituted and unsubstitutedalkylaryl groups, and wherein the alkyl portion thereof can be linear,branched, cyclic, saturated, or unsaturated, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either or both of the aryl portionand the alkyl portion of the alkylaryl group), in one embodiment with atleast about 5 carbon atoms, in another embodiment with at least about 6carbon atoms, and in yet another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 25 carbon atoms, inanother embodiment with no more than about 12 carbon atoms, and in yetanother embodiment with no more than about 7 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as tolyl orthe like, or mixtures thereof, wherein the substituents on thesubstituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (but arenot limited to) hydroxy groups, halogen atoms, amine groups, iminegroups, ammonium groups, cyano groups, pyridine groups, pyridiniumgroups, ether groups, aldehyde groups, ketone groups, ester groups,amide groups, carbonyl groups, thiocarbonyl groups, sulfate groups,sulfonate groups, sulfonic acid groups, sulfide groups, sulfoxidegroups, phosphine groups, phosphonium groups, phosphate groups, nitrilegroups, mercapto groups, nitro groups, nitroso groups, sulfone groups,acyl groups, acid anhydride groups, azide groups, azo groups, cyanatogroups, isocyanato groups, thiocyanato groups, isothiocyanato groups,carboxylate groups, carboxylic acid groups, urethane groups, ureagroups, mixtures thereof, and the like, wherein two or more substituentscan be joined together to form a ring, and p is an integer of 0 or 1,

wherein b is an integer of 0 or 1,

wherein (1) Z is

wherein c is 0 or 1; (2) Ar′ is

(3) G is an alkyl group selected from alkyl groups containing from about2 to about 10 carbon atoms; (4) Ar″ is

wherein s is 0, 1, or 2,

and (6) q is 0 or 1; or mixtures thereof, and n is an integerrepresenting the number of repeat monomer units, (iv) optionally, acompound of the formula

wherein a is an integer of from 1 to 5 and R′ is a hydrogen atom, analkyl group (including linear, branched, cyclic, saturated, unsaturated,substituted, and unsubstituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the alkyl group), in one embodimentwith at least 1 carbon atom, and in one embodiment with no more thanabout 20 carbon atoms, in another embodiment with no more than about 8carbon atoms, and in yet another embodiment with no more than about 4carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an aryl group (including substituted and unsubstitutedaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 4 carbon atoms,in another embodiment with at least about 5 carbon atoms, and in yetanother embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 14 carbon atoms, in anotherembodiment with no more than about 12 carbon atoms, and in yet anotherembodiment with no more than about 10 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an arylalkyl group(including substituted and unsubstituted arylalkyl groups, and whereinthe alkyl portion thereof can be linear, branched, cyclic, saturated, orunsaturated, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the aryl portion and the alkyl portion of thearylalkyl group), in one embodiment with at least about 5 carbon atoms,in another embodiment with at least about 6 carbon atoms, and in yetanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 23 carbon atoms, and in yet anotherembodiment with no more than about 11 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as benzyl or thelike, an alkylaryl group (including substituted and unsubstitutedalkylaryl groups, and wherein the alkyl portion thereof can be linear,branched, cyclic, saturated, or unsaturated, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either or both of the aryl portionand the alkyl portion of the alkylaryl group), in one embodiment with atleast about 5 carbon atoms, in another embodiment with at least about 6carbon atoms, and in yet another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 23 carbon atoms, and in yetanother embodiment with no more than about 11 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as tolyl orthe like, or a mixture thereof, wherein two or more R′ groups can bejoined together to form a ring, wherein the substituents on thesubstituted alkyl, aryl, arylalkyl, and alkylaryl groups can be (but arenot limited to) hydroxy groups, halogen atoms, amine groups, iminegroups, ammonium groups, cyano groups, pyridine groups, pyridiniumgroups, ether groups, aldehyde groups, ketone groups, ester groups,amide groups, carbonyl groups, thiocarbonyl groups, sulfate groups,sulfonate groups, sulfonic acid groups, sulfide groups, sulfoxidegroups, phosphine groups, phosphonium groups, phosphate groups, nitrilegroups, mercapto groups, nitro groups, nitroso groups, sulfone groups,acyl groups, acid anhydride groups, azide groups, azo groups, cyanatogroups, isocyanato groups, thiocyanato groups, isothiocyanato groups,carboxylate groups, carboxylic acid groups, urethane groups, ureagroups, mixtures thereof, and the like, wherein two or more substituentscan be joined together to form a ring, and (v) a carbonate base; and (B)heating the reaction mixture and removing generated water from thereaction mixture, thereby effecting a polymerization reaction.

In the polymers of the above formulae, the phenyl groups and the Aand/or B groups can be either substituted or unsubstituted. Substituentscan be placed thereon either prior to or subsequent to polymerization.Examples of suitable substituents include (but are not limited to) alkylgroups, aryl groups, arylalkyl groups, alkylaryl groups, hydroxy groups,halogen atoms, amine groups, imine groups, ammonium groups, cyanogroups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring.

The polyfunctional phenol material is of the formula Ar(OH)_(x) whereinx≧3 and wherein Ar is an aryl moiety or an alkylaryl moiety, providedthat when Ar is an alkylaryl moiety at least three of the —OH groups arebonded to an aryl portion thereof. Many polyfunctional phenoliccompounds are commercially available, such as1,1,1-tris(4-hydroxyphenyl)ethane (available from Aldrich ChemicalCompany, Mississauga, Ontario), of the formula

Compounds of this type can also be prepared by any desired or effectivemethod. For example, the reaction of anisole with a carboxylic acidchloride (for example propionyl chloride) under standard Friedel-Craftsconditions gives a disubstituted ketone compound (for exampleethyl-(4-methoxyphenyl)ketone). Reaction of this disubstituted ketonewith phenol under acidic (protic) and dehydrating conditions gives a1,1-bis(4-hydroxyphenyl)-1-(4-methoxyphenyl)-substituted methanederivative (for example1,1-bis(4-hydroxyphenyl)-1-(4-methoxyphenyl)-propane). Demethylationusing boron tribromide gives the desired trifunctional1,1,1-tris(4-hydroxyphenyl)-substituted methane derivative (for example1,1,1-tris(4-hydroxyphenyl)-propane). The reaction proceeds as follows:

wherein R_(a) is an alkyl group (including linear, branched, cyclic,saturated, unsaturated, substituted, and unsubstituted alkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the alkylgroup), an aryl group (including substituted and unsubstituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), an arylalkyl group (including substituted andunsubstituted arylalkyl groups, and wherein the alkyl portion thereofcan be linear, branched, cyclic, saturated, or unsaturated, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the arylportion and the alkyl portion of the arylalkyl group), or an alkylarylgroup (including substituted and unsubstituted alkylaryl groups, andwherein the alkyl portion thereof can be linear, branched, cyclic,saturated, or unsaturated, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the aryl portion and the alkylportion of the alkylaryl group).

Higher polyfunctional phenolic compounds can be made in an analogousmanner by the reaction of anisole with an αω-dicarboxylic acid chloride(for example adipoyl chloride) under standard Friedel-Crafts conditionsto give an α,ω-diketone compound (for example1,6-dioxo-1,6-bis(4-methoxyphenyl)hexane)). Reaction of thisα,ω-diketone with phenol under acidic (protic) and dehydratingconditions gives anα,α,ω,ω-tetrakis(4-hydroxyphenyl)-α,ω-bis(4-methoxyphenyl)-substitutedalkane derivative (for example1,1,6,6-tetrakis(4-hydroxyphenyl)-1,6-bis(4-methoxyphenyl)-hexane).Demethylation using boron tribromide gives the desired hexafunctionalα,α,α,ω,ω,ω-hexakis(4-hydroxyphenyl)-substituted alkane derivative (forexample 1,1,1,6,6,6-hexakis(4-hydroxyphenyl)-hexane). The reactionproceeds as follows:

wherein R_(b) is an alkylene group (including linear, branched, cyclic,saturated, unsaturated, substituted, and unsubstituted alkylene groups,and wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in thealkylene group), an arylene group (including substituted andunsubstituted arylene groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the arylene group), an arylalkylene group (includingsubstituted and unsubstituted arylalkylene groups, and wherein the alkylportion thereof can be linear, branched, cyclic, saturated, orunsaturated, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the aryl portion and the alkyl portion of thearylalkylene group), or an alkylarylene group (including substituted andunsubstituted alkylarylene groups, and wherein the alkyl portion thereofcan be linear, branched, cyclic, saturated, or unsaturated, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the arylportion and the alkyl portion of the alkylarylene group).

Even higher polyfunctional phenolic compounds can be made in ananalogous manner by the reaction of anisole with a polycarboxylic acidchloride under standard Friedel-Crafts conditions to give a polyketonecompound. Reaction of this polyketone with phenol under acidic (protic)and dehydrating conditions gives an analogouspoly(4-hydroxyphenyl)/(4-methoxyphenyl) derivative. Demethylation usingboron tribromide gives the desired poly(4-hydroxyphenyl)-substitutedderivative. The reaction proceeds as follows:

wherein R_(c) is an alkyl group (including linear, branched, cyclic,saturated, unsaturated, substituted, and unsubstituted alkyl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the alkylgroup), an aryl group (including substituted and unsubstituted arylgroups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), an arylalkyl group (including substituted andunsubstituted arylalkyl groups, and wherein the alkyl portion thereofcan be linear, branched, cyclic, saturated, or unsaturated, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, andthe like either may or may not be present in either or both of the arylportion and the alkyl portion of the arylalkyl group), or an alkylarylgroup (including substituted and unsubstituted alkylaryl groups, andwherein the alkyl portion thereof can be linear, branched, cyclic,saturated, or unsaturated, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the aryl portion and the alkylportion of the alkylaryl group). Some examples of suitablepolyfunctional phenol compounds include (but are not limited to) thoseof the formula

wherein y is an integer of 1, 2, or 3, z is an integer representing thenumber of HO-φ-CH_(3-y)— groups on R_(d), being in one embodiment atleast 1, and in one embodiment no more than about 10, in anotherembodiment no more than about 3, and in yet another embodiment no morethan about 2, although the value of z can be outside of these ranges,provided that the total number of phenolic groups in the compound is atleast 3, R_(d) is a monovalent moiety, such as (but not limited to) ahydrogen atom, a hydroxy group, a halogen atom, an amine group, an iminegroup, an ammonium group, a cyano group, a pyridine group, a pyridiniumgroup, an ether group, an aldehyde group, a ketone group, an estergroup, an amide group, a carbonyl group, a thiocarbonyl group, a sulfategroup, a sulfonate group, a sulfonic acid group, a sulfide group, asulfoxide group, a phosphine group, a phosphonium group, a phosphategroup, a nitrile group, a mercapto group, a nitro group, a nitrosogroup, a sulfone group, an acyl group, an acid anhydride group, an azidegroup, an azo group, a cyanato group, an isocyanato group, a thiocyanatogroup, an isothiocyanato group, a carboxylate group, a carboxylic acidgroup, a urethane group, a urea group, mixtures thereof, an alkyl group(including linear, branched, cyclic, saturated, unsaturated,substituted, and unsubstituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in the alkyl group), in one embodimentwith at least 1 carbon atom, and in one embodiment with no more thanabout 30 carbon atoms, in another embodiment with no more than about 10carbon atoms, and in yet another embodiment with no more than about 7carbon atoms, although the number of carbon atoms can be outside ofthese ranges, an aryl group (including substituted and unsubstitutedaryl groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present inthe aryl group), in one embodiment with at least about 4 carbon atoms,in another embodiment with at least about 5 carbon atoms, and in yetanother embodiment with at least about 6 carbon atoms, and in oneembodiment with no more than about 30 carbon atoms, in anotherembodiment with no more than about 10 carbon atoms, and in yet anotherembodiment with no more than about 8 carbon atoms, although the numberof carbon atoms can be outside of these ranges, an arylalkyl group(including substituted and unsubstituted arylalkyl groups, and whereinthe alkyl portion thereof can be linear, branched, cyclic, saturated, orunsaturated, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,silicon, phosphorus, and the like either may or may not be present ineither or both of the aryl portion and the alkyl portion of thearylalkyl group), in one embodiment with at least about 5 carbon atoms,in another embodiment with at least about 6 carbon atoms, and in yetanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 30 carbon atoms, in anotherembodiment with no more than about 10 carbon atoms, and in yet anotherembodiment with no more than about 8 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as benzyl or thelike, an alkylaryl group (including substituted and unsubstitutedalkylaryl groups, and wherein the alkyl portion thereof can be linear,branched, cyclic, saturated, or unsaturated, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, and the likeeither may or may not be present in either or both of the aryl portionand the alkyl portion of the alkylaryl group), in one embodiment with atleast about 5 carbon atoms, in another embodiment with at least about 6carbon atoms, and in yet another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 30 carbon atoms, inanother embodiment with no more than about 10 carbon atoms, and in yetanother embodiment with no more than about 8 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as tolyl orthe like, wherein the substituents on the substituted alkyl, aryl,arylalkyl, and alkylaryl groups can be (but are not limited to) hydroxygroups, halogen atoms, amine groups, imine groups, ammonium groups,cyano groups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring,or the like. Other examples of polyfunctional phenol compounds include(but are not limited to) those of the formula

wherein r is an integer of at least about 3, and in one embodiment is nomore than about 10, in another embodiment is no more than about 5, andin yet another embodiment is no more than 3, although the value of r canbe outside of these ranges, and R_(e) is an alkyl group (includinglinear, branched, cyclic, saturated, unsaturated, substituted, andunsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the alkyl group), in one embodiment with at least 1carbon atom, and in one embodiment with no more than about 10 carbonatoms, in another embodiment with no more than about 8 carbon atoms, andin yet another embodiment with no more than about 6 carbon atoms,although the number of carbon atoms can be outside of these ranges, anaryl group (including substituted and unsubstituted aryl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the arylgroup), in one embodiment with at least about 4 carbon atoms, in anotherembodiment with at least about 5 carbon atoms, and in yet anotherembodiment with at least about 6 carbon atoms, and in one embodimentwith no more than about 15 carbon atoms, in another embodiment with nomore than about 10 carbon atoms, and in yet another embodiment with nomore than about 8 carbon atoms, although the number of carbon atoms canbe outside of these ranges, an arylalkyl group (including substitutedand unsubstituted arylalkyl groups, and wherein the alkyl portionthereof can be linear, branched, cyclic, saturated, or unsaturated, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either orboth of the aryl portion and the alkyl portion of the arylalkyl group),in one embodiment with at least about 5 carbon atoms, in anotherembodiment with at least about 6 carbon atoms, and in yet anotherembodiment with at least about 7 carbon atoms, and in one embodimentwith no more than about 15 carbon atoms, in another embodiment with nomore than about 10 carbon atoms, and in yet another embodiment with nomore than about 8 carbon atoms, although the number of carbon atoms canbe outside of these ranges, such as benzyl or the like, or an alkylarylgroup (including substituted and unsubstituted alkylaryl groups, andwherein the alkyl portion thereof can be linear, branched, cyclic,saturated, or unsaturated, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the aryl portion and the alkylportion of the alkylaryl group), in one embodiment with at least about 5carbon atoms, in another embodiment with at least about 6 carbon atoms,and in yet another embodiment with at least about 7 carbon atoms, and inone embodiment with no more than about 15 carbon atoms, in anotherembodiment with no more than about 10 carbon atoms, and in yet anotherembodiment with no more than about 8 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, wherein the substituents on the substituted alkyl, aryl,arylalkyl, and alkylaryl groups can be (but are not limited to) hydroxygroups, halogen atoms, amine groups, imine groups, ammonium groups,cyano groups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring,those of the formula

wherein f is an integer of at least 3 and in one embodiment is no morethan about 6, in another embodiment no more than about 4, and in yetanother embodiment no more than 3, those of the formula

wherein g₁, g₂, g₃, and g₄ are each integers of 0, 1, 2, 3, or 4,provided that the sum of g₁+g₂+g₃+g₄≧3, with the sum of g₁+g₂+g₃+g₄being in one embodiment no more than about 6, in another embodiment nomore than about 4, and in yet another embodiment no more than 3, thoseof the formula

wherein h₁, h₂, h₃, and h₄ are each integers of 0, 1, 2, 3, or 4,provided that the sum of h₁+h₂+h₃+h₄≧3, with the sum of h₁+h₂+h₃+h₄being in one embodiment no more than about 6, in another embodiment nomore than about 4, and in yet another embodiment no more than 3, thoseof the formula

wherein j₁, j₂, j₃, and j₄ are each integers of 0, 1, 2, 3, or 4,provided that the sum of j₁+j₂+j₃+j₄≧3, with the sum of j₁+j₂+j₃+j₄being in one embodiment no more than about 6, in another embodiment nomore than about 4, and in yet another embodiment no more than 3, and thelike. Some specific examples of suitable polyfunctional phenol compoundsinclude (but are not limited to) 1,1,1-tris(4-hydroxyphenyl)ethane, ofthe formula

those of the formula

wherein e is an integer representing the number of repeat —(CH₂)—groups, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, 20, or higher,1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, of the formula

3,3,3′,3′-tetramethyl-1,1′-spirobisindane-5,5′,6,6′-tetrol, of theformula

pyrogallol, of the formula

1,2,4-benzenetriol, of the formula

phloroglucinol dihydrate, of the formula

dithranol, of the formula

nordihydroguaiaretic acid, of the formula

C-methylcalix[4] resorcinarene, of the formula

wherein R is CH₃, C-undecylcalix[4]-resorcinarene monohydrate, of theformula

wherein R is —CH₂(CH₂)₉CH₃, catechin hydrate, of the formula

epicatechin, of the formula

all available from Aldrich Chemical Co., Milwaukee, Wis., and the like,as well as mixtures thereof.

The linear polymer or polymers of the formula

can be obtained commercially. For example, the following materials arecommercially available: ULTRASON™ E3010, BASF Corporation, PlasticsMaterials, Parsippany, N.J., and VICTREX™ PES 4800G, ICI AdvancedMaterials Business Group, Wilmington, Del., both of the Formula

UDEL™ P-1700, Amoco Performance Products Inc., Alpharetta, Ga., andULTRASON™ S2010, BASF Corporation, Plastics Materials, Parsippany, N.J.,both of the formula

RADEL™ R-5000, Amoco Performance Products Inc., Alpharetta, Ga., of theformula

RADEL™ A-200, Amoco Performance Products Inc., Alpharetta, Ga., of theformula

wherein n/m=4.7; ASTREL™360 (x:y=60-70:30-40), 3M Company, ChemicalDivision, St. Paul, Minn., and VICTREX™ 720P (x=y), ICI AdvancedMaterials Business Group, Wilmington, Del., both of the Formula

VICTREX™ HTA, ICI Advanced Materials Business Group, Wilmington, Del.,of the formula

VICTREX™ PEK, ICI Advanced Materials Business Group, Wilmington, Del.,and STILAN™ 1000, Raychem Cooperation, Materials Division, Menlo Park,Calif., both of the formula

VICTREX™ PEEK 450 G, ICI Advanced Materials Business Group, Wilmington,Del., and KADEL™ E-1000, Amoco Performance Products Inc., Alpharetta,Ga., both of the formula

HOSTATEC™, Hoechst AG, 6529 Frankfurt am Main, Germany, of the Formula

ULTRAPEK™ A-2000, BASF AG, D-6700 Ludwigshafen, Germany, of the Formula

PEKK, DuPont Polymers, Specialty Polymers, Wilmington, Del., of theFormula

ULTEM™ 1000, GE Plastics, Pittsfield, Mass., of the formula

and the like. In addition, these linear polymers can be prepared byknown methods, as described in, for example, U.S. Pat. Nos. 5,994,425,6,022,095, 5,849,809, 6,203,143, 6,124,372, 6,151,042, 6,323,301,5,889,077, 6,087,414, 5,739,254, 5,753,783, 5,761,809, 5,958,995,6,184,263, 5,945,253, 6,365,323, 5,863,963, 6,090,453, 6,007,877,6,273,543, 5,814,426, 5,882,814, 5,874,192, 6,117,967, 6,187,512,6,020,119, 6,139,920, 6,260,949, Copending application U.S. Ser. No.10/322,110, Copending application U.S. Ser. No. 10/040,850, Copendingapplication U.S. Ser. No. 10/036,469, and Copending application U.S.Ser. No. 10/717,295, filed Nov. 19, 2003, entitled “Unsaturated EsterSubstituted Polymers with Reduced Halogen Content,” with the namedinventors Christine J. DeVisser and Timothy P. Bender, the disclosuresof each of which are totally incorporated herein by reference.

The reaction can, if desired, be carried out neat in the absence of asolvent, such as in a melt extruder. When an optional solvent is used,the selected solvent can be any polar aprotic solvent suitable for thisparticular reaction. Examples of suitable solvents include (but are notlimited to) N,N-dimethylacetamide, sulfolane (also called tetramethylenesulfone, or TMS), dimethyl formamide, dimethyl sulfoxide,N-methylpyrrolidinone, hexamethylphosphoric triamide (HMPA), and thelike, as well as mixtures thereof.

When present, the optional solvent is present in the reaction mixture inany desired or effective relative amount, in one embodiment at leastabout 1 percent by weight solid reactants in the solvent, in anotherembodiment at least about 5 percent by weight solid reactants in thesolvent, and in yet another embodiment at least about 10 percent byweight solid reactants in the solvent, and in one embodiment no morethan about 75 percent by weight solid reactants in the solvent, inanother embodiment no more than about 50 percent by weight solidreactants in the solvent, and in yet another embodiment no more thanabout 35 percent by weight solid reactants in the solvent, although therelative amount of solvent can be outside of these ranges.

Optionally, if it is desired to have the branched polymer terminatedwith a group other than phenol, the reaction mixture can also contain amaterial of the formula

wherein a is an integer of at least 1, in one embodiment being no morethan about 5, in another embodiment being no more than about 3, and inyet another embodiment being 1 and having the R′ group situated para tothe hydroxy group, R′ is a hydrogen atom, an alkyl group (includinglinear, branched, cyclic, saturated, unsaturated, substituted, andunsubstituted alkyl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in the alkyl group), in one embodiment with at least 1carbon atom, and in one embodiment with no more than about 20 carbonatoms, in another embodiment with no more than about 8 carbon atoms, andin yet another embodiment with no more than about 4 carbon atoms,although the number of carbon atoms can be outside of these ranges, anaryl group (including substituted and unsubstituted aryl groups, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in the arylgroup), in one embodiment with at least about 4 carbon atoms, in anotherembodiment with at least about 5 carbon atoms, and in yet anotherembodiment with at least about 6 carbon atoms, and in one embodimentwith no more than about 14 carbon atoms, in another embodiment with nomore than about 12 carbon atoms, and in yet another embodiment with nomore than about 10 carbon atoms, although the number of carbon atoms canbe outside of these ranges, an arylalkyl group (including substitutedand unsubstituted arylalkyl groups, and wherein the alkyl portionthereof can be linear, branched, cyclic, saturated, or unsaturated, andwherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,phosphorus, and the like either may or may not be present in either orboth of the aryl portion and the alkyl portion of the arylalkyl group),in one embodiment with at least about 5 carbon atoms, in anotherembodiment with at least about 6 carbon atoms, and in yet anotherembodiment with at least about 7 carbon atoms, and in one embodimentwith no more than about 50 carbon atoms, in another embodiment with nomore than about 23 carbon atoms, and in yet another embodiment with nomore than about 11 carbon atoms, although the number of carbon atoms canbe outside of these ranges, such as benzyl or the like, or an alkylarylgroup (including substituted and unsubstituted alkylaryl groups, andwherein the alkyl portion thereof can be linear, branched, cyclic,saturated, or unsaturated, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, and the like either may or maynot be present in either or both of the aryl portion and the alkylportion of the alkylaryl group), in one embodiment with at least about 5carbon atoms, in another embodiment with at least about 6 carbon atoms,and in yet another embodiment with at least about 7 carbon atoms, and inone embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 23 carbon atoms, and in yet anotherembodiment with no more than about 11 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, wherein two or more R′ groups can be joined together to form aring, wherein the substituents on the substituted alkyl, aryl,arylalkyl, and alkylaryl groups can be (but are not limited to) hydroxygroups, halogen atoms, amine groups, imine groups, ammonium groups,cyano groups, pyridine groups, pyridinium groups, ether groups, aldehydegroups, ketone groups, ester groups, amide groups, carbonyl groups,thiocarbonyl groups, sulfate groups, sulfonate groups, sulfonic acidgroups, sulfide groups, sulfoxide groups, phosphine groups, phosphoniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,nitroso groups, sulfone groups, acyl groups, acid anhydride groups,azide groups, azo groups, cyanato groups, isocyanato groups, thiocyanatogroups, isothiocyanato groups, carboxylate groups, carboxylic acidgroups, urethane groups, urea groups, mixtures thereof, and the like,wherein two or more substituents can be joined together to form a ring.Because the alkyl, aryl, arylalkyl, and alkyl groups can includeheteroatoms therein, the possibilities for R′ as defined also includealkoxy groups, aryloxy groups, arylalkyloxy groups, alkylaryloxy groups,polyalkyleneoxy groups, including (but not limited to) those whereineach repeat alkylene oxide unit, independently of the others in thepolyalkyleneoxy group, has in one embodiment at least about 2 carbonatoms, and in one embodiment no more than about 100 carbon atoms, inanother embodiment no more than about 20 carbon atoms, and in yetanother embodiment no more than about 6 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, and wherein thepolyalkyleneoxy group can contain two or more different kinds of repeatalkylene oxide repeat monomer units (such as block or random copolymersof polyethylene oxide and polypropylene oxide or the like), thepolyalkyleneoxy group having in one embodiment at least about 2 repeatalkyleneoxy units, and in one embodiment no more than about 500 repeatalkyleneoxy units, in another embodiment no more than about 10 repeatalkyleneoxy units, and in yet another embodiment no more than about 4repeat alkyleneoxy units, although the number of repeat alkyleneoxyunits can be outside of these ranges. These monofunctional phenols canalso, in some instances, reduce or eliminate crosslinking in thebranched polyarylene ether polymer prepared as disclosed herein.Specific examples of suitable materials of this formula include (but arenot limited to) 2-methyl phenol, 3-methyl phenol, 4-methyl phenol,2-ethyl phenol, 3-ethyl phenol, 4-ethyl phenol, 2-n-propyl phenol,3-n-propyl phenol, 4-n-propyl phenol, 2-isopropyl phenol, 3-isopropylphenol, 4-isopropyl phenol, 2-n-butyl phenol, 3-n-butyl phenol,4-n-butyl phenol, 2-isobutyl phenol, 3-isobutyl phenol, 4-isobutylphenol, 2-sec-butyl phenol, 3-sec-butyl phenol, 4-sec-butyl phenol,2-t-butyl phenol, 3-t-butyl phenol, 4-t-butyl phenol, all possibleisomers (including branched and linear) of pentyl phenol, all possibleisomers (including branched and linear) of hexyl phenol, all possibleisomers (including branched and linear) of heptyl phenol, all possibleisomers (including branched and linear) of octyl phenol, all possibleisomers (including branched and linear) of nonyl phenol, all possibleisomers (including branched and linear) of decyl phenol, all possibleisomers of undecyl phenol, all possible isomers (including branched andlinear) of dodecyl phenol, 2-phenyl phenol, 3-phenyl phenol, 4-phenylphenol, 2-tolyl phenol, 3-tolyl phenol, 4-tolyl phenol, 2-benzyl phenol,3-benzyl phenol, 4-benzyl phenol, 2-methoxy phenol, 3-methoxy phenol,4-methoxy phenol, 2-ethoxy phenol, 3-ethoxy phenol, 4-ethoxy phenol,2-n-propoxy phenol, 3-n-propoxy phenol, 4-n-propoxy phenol, 2-isopropoxyphenol, 3-isopropoxy phenol, 4-isopropoxy phenol, 2-n-butoxy phenol,3-n-butoxy phenol, 4-n-butoxy phenol, 2-isobutoxy phenol, 3-isobutoxyphenol, 4-isobutoxy phenol, 2-sec-butoxy phenol, 3-sec-butoxy phenol,4-sec-butoxy phenol, 2-t-butoxy phenol, 3-t-butoxy phenol, 4-t-butoxyphenol, all possible isomers of pentyloxy phenol, all possible isomers(including branched and linear) of hexyloxy phenol, all possible isomers(including branched and linear) of heptyloxy phenol, all possibleisomers (including branched and linear) of octyloxy phenol, all possibleisomers (including branched and linear) of nonyloxy phenol, all possibleisomers (including branched and linear) of decyloxy phenol, all possibleisomers (including branched and linear) of undecyloxy phenol, allpossible isomers (including branched and linear) of dodecylocy phenol,2-phenoxy phenol, 3-phenoxy phenol, 4-phenoxy phenol, 2-tolyloxy phenol,3-tolyloxy phenol, 4-tolyloxy phenol, 2-benzyloxy phenol, 3-benzyloxyphenol, 4-benzyloxy phenol, 2-(polyethyleneoxy) phenol,3-(polyethyleneoxy) phenol, 4-(polyethyleneoxy) phenol,2-(polypropyleneoxy) phenol, 3-(polypropyleneoxy) phenol,4-(polypropyleneoxy) phenol, 2-(polybutyleneoxy) phenol,3-(polybutyleneoxy) phenol, 4-(polybutyleneoxy) phenol, all2,3-disubstituted variants of the above compounds, all 2,4-disubstitutedvariants of the above compounds, all 2-5-disubstituted variants of theabove compounds, all 2-6-disubstituted variants of the above compounds,all 3,4-disubstituted variants of the above compounds, all3,5-disubstituted variants of the above compounds, all2,3,4-trisubstituted variants of the above compounds, all2,3,5-trisubstituted variants of the above compounds, all2,3,6-trisubstituted variants of the above compounds, all2,4,5-trisubstituted variants of the above compounds, all2,4,6-trisubstituted variants of the above compounds, all3,4,5-trisubstituted variants of the above compounds, all3,4,6-trisubstituted variants of the above compounds, all2,3,4,5-tetrasubstituted variants of the above compounds, all2,3,4,6-tetrasubstituted variants of the above compounds, all2,3,5,6-tetrasubstituted variants of the above compounds, allpentasubstituted variants of the above compounds, mononaphthols, such as1-naphthol and 2-naphthol, and the like, as well as mixtures thereof.

When the optional monophenolic compound of the formula

is present, generally the reaction mixture also contains one or moredihalide monomers of the formula

or mixtures thereof, wherein A and m are as defined hereinabove and Yand Y′ each, independently of the other, is a fluorine atom or achlorine atom. Specific examples of suitable materials of the formula

include (but are not limited to) 4,4′-difluorobenzophenone, of theformula

4,4′-dichlorobenzophenone, of the formula

3,4′-difluorobenzophenone, of the formula

3,4′-dichlorobenzophenone, of the formula

3,3′-difluorobenzophenone, of the formula

3,3′-dichlorobenzophenone, of the formula

2,4′-difluorobenzophenone, of the formula

2,4′-dichlorobenzophenone, of the formula

2,3′-difluorobenzophenone, of the formula

2,3′-dichlorobenzophenone, of the formula

2,2′-difluorobenzophenone, of the formula

2,2′-dichlorobenzophenone, of the formula

compounds of the formulae

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R_(x) is an alkylene group, an arylene group, an arylalkylenegroup, an alkylarylene group, or mixtures thereof,

wherein R_(x) is an alkylene group, an arylene group, an arylalkylenegroup, an alkylarylene group, or mixtures thereof,

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R_(x) is an alkylene group, an arylene group, an arylalkylenegroup, an alkylarylene group, or mixtures thereof,

wherein R_(x) is an alkyl group, an aryl group, an arylalkyl group, analkylaryl group, or mixtures thereof,

and the like. In addition, Y and Y′ need not be the same within amolecule, and one can be fluorine while the other is chlorine, as in thecase of a fluorochlorobenzophenone. Mixtures of two or more compounds ofthis formula can also be employed. In this embodiment, the dihalogenatedcompound is present in the reaction mixture in any desired or effectiveamount, in one embodiment at least about 0.4 mole of dihalogenatedcompound per every one mole of monophenolic phenol compound, and in oneembodiment no more than about 0.6 mole of dihalogenated compound perevery one mole of monophenolic phenol compound, although the relativeamounts can be outside of these ranges.

A dihalogenated monomer of the formula

or mixtures thereof can also be added to the reaction mixture even inthe absence of a monophenolic endcapping compound if it is desired toterminate the branched polymers with groups other than phenolic groupsor those corresponding to the monophenolic endcapping compound. Forexample, halogen-terminated polymers can be prepared by including in thereaction mixture one or more dihalogenated monomers in an amountcorresponding stoichiometrically to the polyfunctional phenol functionalgroups. For example, when the polyfunctional phenol is a trifunctionalphenol, in one embodiment, at least about 1.4 moles of dihalogenatedmonomers are present per every one mole of trifunctional phenol, and inanother embodiment no more than about 1.6 moles of dihalogenatedmonomers are present per every one mole of trifunctional phenol,although the relative amounts can be outside of these ranges.

The reaction mixture also contains a carbonate base. The carbonate basecan be any desired material, such as lithium carbonate, sodiumcarbonate, potassium carbonate, cesium carbonate, or the like. Thecarbonate base is present in the reaction mixture in any desired oreffective amount, generally in a molar excess with respect to thepolyfunctional phenol and, if present, the optional monophenol. Forexample, the carbonate base can be present in an amount of in oneembodiment at least about 10 moles of carbonate base per every mole ofpolyfunctional phenol, in another embodiment at least about 25 moles ofcarbonate base per every mole of polyfunctional phenol, and in yetanother embodiment at least about 50 moles of carbonate base per everymole of polyfunctional phenol, although the amount can be outside ofthese ranges. When the optional monophenol is present, an additionalamount of polycarbonate can be added in an amount of in one embodimentat least about 3 moles of carbonate base per every one mole ofmonofunctional phenol, in another embodiment at least about 8 moles ofcarbonate base per every one mole of monofunctional phenol, and in yetanother embodiment at least about 16 moles of carbonate base per everyone mole of monofunctional phenol, although the amount can be outside ofthese ranges.

Further information regarding the optional end-capping additive and thecarbonate base are disclosed in, for example, Copending Application U.S.Ser. No. 10/040,850, the disclosure of which is totally incorporatedherein by reference.

The material of the formula Ar(OH)_(x), the polymer or polymers of theformula

and, if present, the optional material of the formula

are each present in the reaction mixture in any desired or effectiveamounts, in one embodiment such that the total solids content (i.e. thesum total amount of each of these three materials) in the reactionmixture is at least about 1 percent by weight solids content, in anotherembodiment at least about 20 percent by weight solids content, and inyet another embodiment at least about 25 percent by weight solidscontent, and in one embodiment no more than about 75 percent by weightsolids content, in another embodiment no more than about 50 percent byweight solids content, and in yet another embodiment no more than about45 percent by weight solids content, although the solids content of thereaction mixture can be outside of these ranges.

The reaction mixture is heated to any effective temperature for reactionto take place. When an optional solvent is used, for example, thetemperature can be that at which reflux occurs. This temperaturegenerally depends on the solvent employed and on the pressure at whichthe reaction is carried out. For example, when carried out at 1atmosphere of pressure with an N,N-dimethylacetamide solvent, thereaction temperature is in one embodiment at least about 145° C., inanother embodiment at least about 155° C., and in yet another embodimentat least about 160° C., and in one embodiment no more than about 200°C., in another embodiment no more than about 180° C., and in yet anotherembodiment no more than about 170° C., although the temperature can beoutside of these ranges.

Heating of the reaction mixture occurs for any period of time effectiveto complete the polymerization reaction. Completion of the reaction canbe determined when 3 consecutive samples of polymer taken from thereactor at periods of from about 10 to about 30 minutes apart exhibitabout the same molecular weight value (±about 500 Daltons) and about thesame polydispersity value (±about 2). Reaction times are in oneembodiment at least about 4 hours, in another embodiment at least about6 hours, and in yet another embodiment at least about 8 hours, and inone embodiment no more than about 10 hours, in another embodiment nomore than about 9 hours, and in yet another embodiment no more thanabout 8.5 hours, although the reaction time can be outside of theseranges.

Water is generated during the reaction, and this water is removed fromthe reaction mixture because of the instability of phenoxide compoundsin the presence of water. One method of removing water is by azeotropicdistillation with a solvent such as toluene. Any other desired oreffective method for removing water from the reaction mixture can alsobe employed. The toluene is present in the reaction mixture in anyeffective amount, in one embodiment at least about 1 percent by weightof the reactor contents, and in another embodiment at least about 12percent by weight of the reactor contents, and in one embodiment no morethan about 30 percent by weight of the reactor contents, and in anotherembodiment no more than about 15 percent by weight of the reactorcontents, although the amount of toluene can be outside of these ranges.

The polymer formed by the process disclosed herein can be of any desiredmolecular weight. In one specific embodiment, the weight averagemolecular weight (M_(w)) in Daltons is in one embodiment at least about2,000 in another embodiment at least about 4,000, and in yet anotherembodiment at least about 8,000, and in one embodiment no more thanabout 500,000, in another embodiment no more than about 250,000, and inyet another embodiment no more than about 100,000, although the weightaverage molecular weight can be outside of these ranges. The numberaverage molecular weight (Mn) is in one embodiment at least about 2,000,in another embodiment at least about 4,000, and in yet anotherembodiment at least about 8,000, and in one embodiment no more thanabout 500,000, in another embodiment no more than about 250,000, and inyet another embodiment no more than about 100,000, although the numberaverage molecular weight can be outside of these ranges.

Molecular weight values recited herein are values measured using gelpermeation chromatography and are relative to polystyrene standards.

The polyfunctional phenol material of the formula Ar(OH)_(x) and thelinear polymer or polymers of the formula

are present in the reaction mixture in any desired or effective relativeamounts. The ratio of linear polymer to polyfunctional phenol materialis in one embodiment at least about 2 moles of linear polymer per everyone mole of polyfunctional phenol material, in another embodiment atleast about 5 moles of linear polymer per every one mole ofpolyfunctional phenol material, and in yet another embodiment at leastabout 10 moles of linear polymer per every one mole of polyfunctionalphenol material, and in one embodiment no more than about 250 moles oflinear polymer per every one mole of polyfunctional phenol material, inanother embodiment no more than about 175 moles of linear polymer perevery one mole of polyfunctional phenol material, and in yet anotherembodiment no more than about 100 moles of linear polymer per every onemole of polyfunctional phenol material, although the relative amounts oflinear polymer and polyfunctional phenol material can be outside ofthese ranges.

When an optional monofunctional phenol compound is present in thereaction mixture, the polyfunctional phenol material of the formulaAr(OH)_(x) and the monofunctional phenol compound of the formula

are present in the reaction mixture in any desired or effective relativeamounts. The ratio of polyfunctional phenol material to monofunctionalphenol is in one embodiment at least about 0.1 mole of polyfunctionalphenol material per every one mole of monofunctional phenol, in anotherembodiment at least about 0.25 mole of polyfunctional phenol materialper every one mole of monofunctional phenol, and in yet anotherembodiment at least about 0.33 mole of polyfunctional phenol materialper every one mole of monofunctional phenol, and in one embodiment nomore than about 1 mole of polyfunctional phenol material per every onemole of monofunctional phenol, in another embodiment no more than about0.66 mole of polyfunctional phenol material per every one mole ofmonofunctional phenol, and in yet another embodiment no more than about0.5 mole of polyfunctional phenol material per every one mole ofmonofunctional phenol, although the relative amounts of polyfunctionalphenol material and monofunctional phenol can be outside of theseranges.

When an optional monofunctional phenol compound is present in thereaction mixture, the linear polymer of the formula

and the monofunctional phenol compound of the formula

are present in the reaction mixture in any desired or effective relativeamounts. The ratio of linear polymer to monofunctional phenol is in oneembodiment at least about 2 moles of linear polymer per every one moleof monofunctional phenol, in another embodiment at least about 4 molesof linear polymer per every one mole of monofunctional phenol, and inyet another embodiment at least about 6 moles of linear polymer perevery one mole of monofunctional phenol, and in one embodiment no morethan about 10 moles of linear polymer per every one mole ofmonofunctional phenol, in another embodiment no more than about 8 molesof linear polymer per every one mole of monofunctional phenol, and inyet another embodiment no more than about 7 moles of linear polymer perevery one mole of monofunctional phenol, although the relative amountsof linear polymer and monofunctional phenol can be outside of theseranges.

While not being limited to any particular theory, it is believed thatformation of the branched portions of the polymer occurs when thecarbonate base (potassium carbonate in the illustrated examples) reactswith the hydroxy groups on the polyfunctional phenol compound to form asalt:

Thereafter, the polyfunctional phenol compound initiates a nucleophilicaromatic substitution reaction with halogen-terminated endgroups on thelinear polymers, as follows (illustrated in the following examples forthe situation wherein Y is a fluorine atom):

For example, when the “A” group is >C═O, m is 1, and the bond betweenthe phenyl group and the “A” group is para to the fluorine atom, thisprocess occurs as follows:

The polyfunctional phenol compound thus becomes bonded through theoxygen atom to the phenyl ring on the “A” moiety:

and a branched moiety is formed:

When the optional monophenolic compound is present, the reactioninvolving the endcapping monophenolic compound (illustrated here for acompound having a single R′ group) is believed to proceed by a similarmechanism:

It is also believed that the polyfunctional phenol compound of theformula Ar(OH)_(x), any phenol-terminated linear polymers, and themonophenolic compound can each initiate a chain cleavage reaction withlinear polymer chains, as follows (with all three reactants generalizedin the illustrated reaction mechanism as a square with an attachedanionic oxygen atom):

Again, while not being limited to any particular theory, it is believedthat the polyfunctional phenol compound, any phenol-terminated linearpolymers, and the monophenolic compound all react freely with anyhalogen-terminated linear polymers, and that there is a constantscrambling of the polymeric chains in an equilibrium state of chainscission and recombination. Accordingly, the entire branched polymerreaches a state of equilibrium under the polymerization conditions. Inaddition, the optional monofunctional phenol endcapping agent workseffectively even if it is added at the beginning of the reaction, and itdoes not broaden the molecular weight distribution of the system.Further, the optional monofunctional phenol can control thepolydispersity and the molecular weight of the resulting polymer byestablishment of an equilibrium that balances all of the thermodynamicforces at play in the system. The molecular weight of the branchedpolyarylene ethers prepared by the process of the present invention canbe controlled by varying the stoichiometry of the starting materials,and during the process the molecular weight reaches a nearly constantvalue after which it neither rises further nor falls further.

The resulting absolute molecular weight of the branched polymer thusformed will very likely not change from that of the linear polymer orpolymers used as starting materials, but the measured molecular weightby gas phase chromatography, as indicated by a longer retention time,will very likely decrease, since the hydrodynamic volume of a branchedpolymer tends to be less than the hydrodynamic volume of its linearanalog. The magnitude of the measured decrease in hydrodynamic volumewill tend to be proportional to the number of branched points in thepolymer.

It is believed that the polymers formed by this process are branchedpolyarylene ether polymers which comprise a plurality of branch points,each branch point being of the formula

wherein each Ar, independently of the others, is an aryl moiety or analkylaryl moiety, provided that when Ar is an alkylaryl moiety at leastthree

repeating groups are bonded to an aryl portion thereof through theoxygen atoms in the repeating groups, each x, independently of theothers, is an integer of 3 or greater, each m, independently of theothers, is an integer of 0 or 1, each D, independently of the others, iseither (a) another branch point, (b) a terminal group, or (c) of theformula

wherein each n, independently of the others, is an integer representingthe number of repeat monomer units, each A, independently of the others,is

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R_(x) is an alkylene group, an arylene group, an arylalkylenegroup, an alkylarylene group, or mixtures thereof,

mixtures thereof, each B, independently of the others, is

wherein z is an integer of from 2 to about 20,

wherein u is an integer of from 1 to about 20,

wherein w is an integer of from 1 to about 20,

wherein each o, independently of the other, is an integer of 1, 2, 3, or4,

wherein R₁ and R₂ each, independently of the other, are hydrogen atoms,alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, ormixtures thereof, and p is an integer of 0 or 1,

wherein b is an integer of 0 or 1,

wherein (1) Z is

wherein c is 0 or 1; (2) Ar′ is

(3) G is an alkyl group selected from alkyl groups containing from about2 to about 10 carbon atoms; (4) Ar″ is

wherein s is 0, 1, or 2,

and (6) q is 0 or 1; or mixtures thereof. It is believed that thesebranched polyarylene ether polymers are of the formula

wherein each Ar, independently of the others, is an aryl moiety or analkylaryl moiety, provided that when Ar is an alkylaryl moiety at leastthree

repeating groups are bonded to an aryl portion thereof through theoxygen atoms in the repeating groups, each x, independently of theothers, is an integer of 3 or greater, each k and each n, independentlyof the others, are integers representing the number of repeat monomerunits, each W, independently of the others, is

wherein each m, independently of the others, is an integer of 0 or 1,each A, independently of the others, is

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R_(x) is an alkylene group, an arylene group, an arylalkylenegroup, an alkylarylene group, or mixtures thereof,

or mixtures thereof, each B, independently of the others, is

wherein z is an integer of from 2 to about 20,

wherein u is an integer of from 1 to about 20,

wherein w is an integer of from 1 to about 20,

wherein each o, independently of the other, is an integer of 1, 2, 3, or4,

wherein R₁ and R₂ each, independently of the other, are hydrogen atoms,alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, ormixtures thereof, and p is an integer of 0 or 1,

wherein b is an integer of 0 or 1,

wherein (1) Z is

wherein c is 0 or 1; (2) Ar′ is

(3) G is an alkyl group selected from alkyl groups containing from about2 to about 10 carbon atoms; (4) Ar″ is

wherein s is 0, 1, or 2,

and (6) q is 0 or 1; or mixtures thereof.

Also disclosed herein are imaging members which comprise a conductivesubstrate, a photogenerating material, and a binder which comprises apolymer prepared as disclosed herein. Examples of suitable imagingmember configurations are illustrated in the Figures of, for example,U.S. Pat. No. 6,174,636, the disclosure of which is totally incorporatedherein by reference.

The substrate can be formulated entirely of an electrically conductivematerial, or it can be an insulating material having an electricallyconductive surface. The substrate is of any desired or effectivethickness, generally up to about 100 mils, and in one embodiment fromabout 1 to about 50 mils, although the thickness can be outside of thisrange. The thickness of the substrate layer depends on many factors,including economic and mechanical considerations. Thus, this layer canbe of substantial thickness, for example over 100 mils, or of minimalthickness provided that there are no adverse effects on the system.Similarly, the substrate can be either rigid or flexible. In a specificembodiment, the thickness of this layer is from about 3 mils to about 10mils. For flexible belt imaging members, substrate thicknesses include(but are not limited to) those from about 65 to about 150 microns, andin a more specific embodiment from about 75 to about 100 microns foroptimum flexibility and minimum stretch when cycled around smalldiameter rollers of, for example, 19 millimeter diameter.

The substrate can be opaque or substantially transparent and cancomprise numerous suitable materials having the desired mechanicalproperties. The entire substrate can comprise the same material as thatin the electrically conductive surface or the electrically conductivesurface can be merely a coating on the substrate. Any suitableelectrically conductive material can be employed. Examples ofelectrically conductive materials include copper, brass, nickel, zinc,chromium, stainless steel, conductive plastics and rubbers, aluminum,semitransparent aluminum, steel, cadmium, silver, gold, zirconium,niobium, tantalum, vanadium, hafnium, titanium, nickel, chromium,tungsten, molybdenum, paper rendered conductive by the inclusion of asuitable material therein or through conditioning in a humid atmosphereto ensure the presence of sufficient water content to render thematerial conductive, indium, tin, metal oxides, including tin oxide andindium tin oxide, and the like. The conductive layer can vary inthickness over substantially wide ranges depending on the desired use ofthe electrophotoconductive member. Generally, the conductive layerranges in thickness from about 50 Angstroms to many centimeters,although the thickness can be outside of this range. When a flexibleelectrophotographic imaging member is desired, the thickness of theconductive layer in one embodiment is from about 20 Angstroms to about750 Angstroms, and in another embodiment is from about 100 to about 200Angstroms for an optimum combination of electrical conductivity,flexibility, and light transmission. When the 1.0 selected substratecomprises a nonconductive base and an electrically conductive layercoated thereon, the substrate can be of any other conventional material,including organic and inorganic materials. Examples of substratematerials include insulating non-conducting materials such as variousresins known for this purpose including polycarbonates, polyamides,polyurethanes, paper, glass, plastic, polyesters such as MYLAR(available from DuPont) or MELINEX 447 (available from ICI Americas,Inc.), and the like. The conductive layer can be coated onto the baselayer by any suitable coating technique, such as vacuum deposition orthe like. If desired, the substrate can comprise a metallized plastic,such as titanized or aluminized MYLAR, wherein the metallized surface isin contact with the photogenerating layer or any other layer situatedbetween the substrate and the photogenerating layer. The coated oruncoated substrate can be flexible or rigid, and can have any number ofconfigurations, such as a plate, a cylindrical drum, a scroll, anendless flexible belt, or the like. The outer surface of the substratecan comprise a metal oxide such as aluminum oxide, nickel oxide,titanium oxide, or the like.

The photoconductive imaging member can optionally contain a chargeblocking layer situated between the conductive substrate and thephotogenerating layer. Generally, electron blocking layers forpositively charged photoreceptors allow holes from the imaging surfaceof the photoreceptor to migrate toward the conductive layer, while holeblocking layers for negatively charged photoreceptors allow electronsfrom the imaging surface of the photoreceptor to migrate toward theconductive layer. This layer can comprise metal oxides, such as aluminumoxide and the like, or materials such as silanes and nylons, nitrogencontaining siloxanes or nitrogen containing titanium compounds such astrimethoxysilyl propylene diamine, hydrolyzed trimethoxysilyl propylethylene diamine, N-beta-(aminoethyl) gamma-amino-propyl trimethoxysilane, isopropyl 4-aminobenzene sulfonyl, di(dodecylbenzene sulfonyl)titanate, isopropyl di(4-aminobenzoyl)isostearoyl titanate, isopropyltri(N-ethylamino-ethylamino)titanate, isopropyl trianthranil titanate,isopropyl tri(N,N-dimethyl-ethylamino)titanate, titanium-4-amino benzenesulfonate oxyacetate, titanium 4-aminobenzoate isostearate oxyacetate,[H₂N(CH₂)₄]CH₃Si(OCH₃)₂, (gamma-aminobutyl) methyl diethoxysilane, and[H₂N(CH₂)₃]CH₃Si(OCH₃)₂ (gamma-aminopropyl) methyl diethoxysilane, asdisclosed in U.S. Pat. Nos. 4,291,110, 4,338,387, 4,286,033 and4,291,110, the disclosures of each of which are totally incorporatedherein by reference, or the like. Additional examples of suitablematerials include gelatin (e.g. GELATIN 225, available from KnoxGelatine Inc.), and/or CARBOSET 515 (B.F. Goodrich Chemical Company)dissolved in water and methanol, polyvinyl alcohol, polyamides,gamma-aminopropyl triethoxysilane, polyisobutyl methacrylate, copolymersof styrene and acrylates such as styrene/n-butyl methacrylate,copolymers of styrene and vinyl toluene, polycarbonates, alkylsubstituted polystyrenes, styrene-olefin copolymers, polyesters,polyurethanes, polyterpenes, silicone elastomers, mixtures or blendsthereof, copolymers thereof, and the like. One specific blocking layercomprises a reaction product between a hydrolyzed silane and theoxidized surface of a metal ground plane layer. The oxidized surfaceinherently forms on the outer surface of most metal ground plane layerswhen exposed to air after deposition. The primary purpose of this layeris to prevent charge injection from the substrate during and aftercharging. This layer is in one embodiment of a thickness of less than 50Angstroms to about 10 microns, in another embodiment being no more thanabout 2 microns, and in yet another embodiment being no more than about0.2 microns, although the thickness can be outside these ranges.

The blocking layer can be applied by any suitable conventional techniquesuch as spraying, dip coating, draw bar coating, gravure coating, silkscreening, air knife coating, reverse roll coating, vacuum deposition,chemical treatment or the like. For convenience in obtaining thinlayers, the blocking layers can be applied in the form of a dilutesolution, with the solvent being removed after deposition of the coatingby conventional techniques such as by vacuum, heating and the like.

In some cases, intermediate adhesive layers between the substrate andsubsequently applied layers can be desirable to improve adhesion. Ifsuch adhesive layers are utilized, they can have a dry thickness in oneembodiment of from about 0.1 micron to about 5 microns, although thethickness can be outside of this range. Examples of adhesive layersinclude film-forming polymers such as polyesters, polyvinylbutyrals,polyvinylpyrrolidones, polycarbonates, polyurethanes,polymethylmethacrylates, DUPONT 49,000 (available from E.I. duPont deNemours and Company), VITEL PE100 (available from Goodyear Tire &Rubber), and the like as well as mixtures thereof. The branched polymersdisclosed herein can also be employed in the adhesive layer of theimaging member, either alone or in combination with other materials.Since the surface of the substrate can be a charge blocking layer or anadhesive layer, the expression “substrate” as employed herein isintended to include a charge blocking layer with or without an adhesivelayer on a charge blocking layer. Adhesive layer thicknesses are in oneembodiment from about 0.05 micron (500 Angstroms) to about 0.3 micron(3,000 Angstroms), although the thickness can be outside of this range.Conventional techniques for applying an adhesive layer coating mixtureto the substrate include spraying, dip coating, roll coating, wire woundrod coating, gravure coating, Bird bar applicator coating, slot coating,or the like. Drying of the deposited coating can be effected by anysuitable conventional technique, such as oven drying, infra redradiation drying, air drying, or the like.

The photogenerating layer can comprise single or multiple layerscomprising inorganic or organic compositions and the like. One exampleof a generator layer is described in U.S. Pat. No. 3,121,006, thedisclosure of which is totally incorporated herein by reference, whereinfinely divided particles of a photoconductive inorganic compound aredispersed in an electrically insulating organic resin binder.Multi-photogenerating layer compositions can be utilized where aphotoconductive layer enhances or reduces the properties of thephotogenerating layer. Examples of this type of configuration aredescribed in U.S. Pat. No. 4,415,639, the disclosure of which is totallyincorporated herein by reference. Further examples of photosensitivemembers having at least two electrically operative layers include thecharge generator layer and diamine containing transport layer membersdisclosed in U.S. Pat. Nos. 4,265,990, 4,233,384, 4,306,008, and4,299,897, the disclosures of each of which are totally incorporatedherein by reference; dyestuff generator layer and oxadiazole,pyrazalone, imidazole, bromopyrene, nitrofluorene and nitronaphthalimidederivative containing charge transport layers members, as disclosed inU.S. Pat. No. 3,895,944, the disclosure of which is totally incorporatedherein by reference; generator layer and hydrazone containing chargetransport layers members, disclosed in U.S. Pat. No. 4,150,987, thedisclosure of which is totally incorporated herein by reference;generator layer and a tri-aryl pyrazoline compound containing chargetransport layer members, as disclosed in U.S. Pat. No. 3,837,851, thedisclosure of which is totally incorporated herein by reference; and thelike.

The photogenerating or photoconductive layer contains any desired orsuitable photoconductive material. The photoconductive layer or layerscan contain inorganic or organic photoconductive materials. Examples ofinorganic photoconductive materials include amorphous selenium, trigonalselenium, alloys of selenium with elements such as tellurium, arsenic,and the like, amorphous silicon, cadmium sulfoselenide, cadmiumselenide, cadmium sulfide, zinc oxide, titanium dioxide, and the like.Inorganic photoconductive materials can, if desired, be dispersed in afilm forming polymer binder.

Examples of organic photoconductors include various phthalocyaninepigments, such as the X-form of metal free phthalocyanine described inU.S. Pat. No. 3,357,989, the disclosure of which is totally incorporatedherein by reference, metal phthalocyanines such as vanadylphthalocyanine, copper phthalocyanine, and the like, quinacridones,including those available from DuPont as Monastral Red, Monastral Violetand Monastral Red Y, substituted 2,4-diamino-triazines as disclosed inU.S. Pat. No. 3,442,781, the disclosure of which is totally incorporatedherein by reference, polynuclear aromatic quinones, Indofast Violet LakeB, Indofast Brilliant Scarlet, Indofast Orange, dibromoanthanthronessuch as those available from DuPont as Vat orange 1 and Vat orange 3,squarylium, pyrazolones, polyvinylcarbazole-2,4,7-trinitrofluorenone,anthracene, benzimidazole perylene, polynuclear aromatic quinonesavailable from Allied Chemical Corporation under the tradename IndofastDouble Scarlet, Indofast Violet Lake B, Indofast Brilliant Scarlet andIndofast Orange, and the like. Many organic photoconductor materials canalso be used as particles dispersed in a resin binder.

Examples of suitable binders for the photoconductive materials includethermoplastic and thermosetting resins such as polycarbonates,polyesters, including polyethylene terephthalate, polyurethanes,polystyrenes, polybutadienes, polysulfones, polyarylethers,polyarylsulfones, polyethersulfones, polyethylenes, polypropylenes,polymethylpentenes, polyphenylene sulfides, polyvinyl acetates,polyvinylbutyrals, polysiloxanes, polyacrylates, polyvinyl acetals,polyamides, polyimides, amino resins, phenylene oxide resins,terephthalic acid resins, phenoxy resins, epoxy resins, phenolic resins,polystyrene and acrylonitrile copolymers, polyvinylchlorides, polyvinylalcohols, poly-(N-vinylpyrrolidinone)s, vinylchloride and vinyl acetatecopolymers, acrylate copolymers, alkyd resins, cellulosic film formers,poly(amideimide), styrene-butadiene copolymers,vinylidenechloride-vinylchloride copolymers,vinylacetate-vinylidenechloride copolymers, styrene-alkyd resins,polyvinylcarbazoles, and the like. These polymers can be block, randomor alternating copolymers. The branched polymers as disclosed herein canalso be employed in the photoconductive layer of the imaging member,either alone or in combination with other materials.

When the photogenerating material is present in a binder material, thephotogenerating composition or pigment can be present in the filmforming polymer binder compositions in any suitable or desired amounts.For example, in one embodiment from about 10 percent by volume to about60 percent by volume of the photogenerating pigment can be dispersed inabout 40 percent by volume to about 90 percent by volume of the filmforming polymer binder composition, and in another embodiment from about20 percent by volume to about 30 percent by volume of thephotogenerating pigment can be dispersed in about 70 percent by volumeto about 80 percent by volume of the film forming polymer bindercomposition. The photoconductive material is present in thephotogenerating layer in an amount in one embodiment of from about 5 toabout 80 percent by weight, and in another embodiment from about 25 toabout 75 percent by weight, and the binder is present in an amount inone embodiment of from about 20 to about 95 percent by weight, and inanother embodiment from about 25 to about 75 percent by weight, althoughthe relative amounts can be outside these ranges.

The particle size of the photoconductive compositions and/or pigments inone embodiment is less than the thickness of the deposited solidifiedlayer, and in another embodiment is between about 0.01 micron and about0.5 micron to facilitate better coating uniformity.

The photogenerating layer containing photoconductive compositions andthe resinous binder material in one embodiment ranges in thickness fromabout 0.05 micron to about 10 microns or more, in another embodimentbeing from about 0.1 micron to about 5 microns, and in yet anotherembodiment having a thickness of from about 0.3 micron to about 3microns, although the thickness can be outside these ranges. Thephotogenerating layer thickness is related to the relative amounts ofphotogenerating compound and binder, with the photogenerating materialoften being present in amounts of from about 5 to about 100 percent byweight. Higher binder content compositions generally require thickerlayers for photogeneration. Generally, it is desirable to provide thislayer in a thickness sufficient to absorb about 90 percent or more ofthe incident radiation which is directed upon it in the imagewise orprinting exposure step. The maximum thickness of this layer is dependentprimarily upon factors such as mechanical considerations, the specificphotogenerating compound selected, the thicknesses of the other layers,and whether a flexible photoconductive imaging member is desired.

The photogenerating layer can be applied to underlying layers by anydesired or suitable method. Any suitable technique can be utilized tomix and thereafter apply the photogenerating layer coating mixture.Examples of application techniques include spraying, dip coating, rollcoating, wire wound rod coating, and the like. Drying of the depositedcoating can be effected by any suitable technique, such as oven drying,infra red radiation drying, air drying, and the like.

Any other suitable multilayer photoconductors can also be employed inthe imaging member. Some multilayer photoconductors comprise at leasttwo electrically operative layers, a photogenerating or chargegenerating layer and a charge transport layer. The charge generatinglayer and charge transport layer as well as the other layers can beapplied in any suitable order to produce either positive or negativecharging photoreceptors. For example, the charge generating layer can beapplied prior to the charge transport layer, as illustrated in U.S. Pat.No. 4,265,990, or the charge transport layer can be applied prior to thecharge generating layer, as illustrated in U.S. Pat. No. 4,346,158, theentire disclosures of these patents being incorporated herein byreference.

When present, the optional charge transport layer can comprise anysuitable charge transport material. The active charge transport layercan consist entirely of the desired charge transport material, or cancomprise an activating compound useful as an additive dispersed inelectrically inactive polymeric materials making these materialselectrically active. These compounds can be added to polymeric materialswhich are incapable of supporting the injection of photogenerated holesfrom the generation material and incapable of allowing the transport ofthese holes therethrough, thereby converting the electrically inactivepolymeric material to a material capable of supporting the injection ofphotogenerated holes from the generation material and capable ofallowing the transport of these holes through the active layer in orderto discharge the surface charge on the active layer. One specifictransport layer comprises from about 25 percent to about 75 percent byweight of at least one charge transporting compound, and from about 75percent to about 25 percent by weight of a polymeric film forming resinin which the aromatic amine is soluble.

Examples of charge transport materials include pure selenium,selenium-arsenic alloys, selenium-arsenic-halogen alloys,selenium-halogen, and the like. Generally, from about 10 parts by weightper million to about 200 parts by weight per million of halogen arepresent in a halogen doped selenium charge transport layer, although theamount can be outside of this range. If a halogen doped transport layerfree of arsenic is utilized, the halogen content in one embodiment isless than about 20 parts by weight per million. Transport layers arewell known in the art. Examples of transport layers are described, forexample, in U.S. Pat. No. 4,609,605 and in U.S. Pat. No. 4,297,424, thedisclosures of each of these patents being totally incorporated hereinby reference.

Organic charge transport materials can also be employed. Examples ofcharge transporting materials include the following:

Diamine transport molecules of the type described in U.S. Pat. Nos.4,306,008, 4,304,829, 4,233,384, 4,115,116, 4,299,897, 4,265,990, and4,081,274, the disclosures of each of which are totally incorporatedherein by reference. Examples of diamine transport molecules includeN,N′-diphenyl-N,N′-bis(3″-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine,N,N′-diphenyl-N,N′-bis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine,N,N′-diphenyl-N,N′-bis(2-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine,N,N′-diphenyl-N,N′-bis(3-ethylphenyl)-(1,1′-biphenyl)-4,4′-diamine,N,N′-diphenyl-N,N′-bis(4-ethylphenyl)-(1,1′-biphenyl)-4,4′-diamine,N,N′-diphenyl-N,N′-bis(4-n-butylphenyl)-(1,1′-biphenyl)-4,4′-diamine,N,N′-diphenyl-N,N′-bis(3-chlorophenyl)-[1,1′-biphenyl]-4,4′-diamine,N,N′-diphenyl-N,N′-bis(4-chlorophenyl)-[1,1′-biphenyl]-4,4′-diamine,N,N′-diphenyl-N,N′-bis(phenylmethyl)-[1,1′-biphenyl]-4,4′-diamine,N,N,N′,N′-tetraphenyl-[2,2′-dimethyl-1,1′-biphenyl]-4,4′-diamine,N,N,N′,N′-tetra-(4-methylphenyl)-[2,2′-dimethyl-1,1′-biphenyl]-4,4′-diamine,N,N′-diphenyl-N,N′-bis(4-methylphenyl)-[2,2′-dimethyl-1,1′-biphenyl]-4,4′-diamine,N,N′-diphenyl-N,N′-bis(2-methylphenyl)-[2,2′-dimethyl-1,1′-biphenyl]-4,4′-diamine,N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[2,2′-dimethyl-1,1′-biphenyl]-4,4′-diamine,N,N′-diphenyl-N,N′-bis(3-methylphenyl)-pyrenyl-1,6-diamine, and thelike.

Pyrazoline transport molecules as disclosed in U.S. Pat. Nos. 4,315,982,4,278,746, and 3,837,851, the disclosures of each of which are totallyincorporated herein by reference. Examples of pyrazoline transportmolecules include1-[lepidyl-(2)]-3-(p-diethylaminophenyl)-5-(p-diethylaminophenyl)pyrazoline,1-[quinolyl-(2)]-3-(p-diethylaminophenyl)-5-(p-diethylaminophenyl)pyrazoline,1-[pyridyl-(2)]-3-(p-diethylaminostyryl)-5-(p-diethylaminophenyl)pyrazoline,1-[6-methoxypyridyl-(2)]-3-(p-diethylaminostyryl)-5-(p-diethylaminophenyl)pyrazoline, 1-phenyl-3-[p-dimethylaminostyryl]-5-(p-dimethylaminostyryl)pyrazoline,1-phenyl-3-[p-diethylaminostyryl]-5-(p-diethylaminostyryl)pyrazoline,and the like.

Substituted fluorene charge transport molecules as described in U.S.Pat. No. 4,245,021, the disclosure of which is totally incorporatedherein by reference. Examples of fluorene charge transport moleculesinclude 9-(4′-dimethylaminobenzylidene)fluorene,9-(4′-methoxybenzylidene)fluorene,9-(2′,4′-dimethoxybenzylidene)fluorene, 2-nitro-9-benzylidene-fluorene,2-nitro-9-(4′-diethylaminobenzylidene)fluorene, and the like.

Oxadiazole transport molecules such as2,5-bis(4-diethylaminophenyl)-1,3,4-oxadiazole, pyrazoline, imidazole,triazole, and the like. Other examples of oxadiazole transport moleculesare described, for example, in German Patent 1,058,836, German Patent1,060,260, and German Patent 1,120,875, the disclosures of each of whichare totally incorporated herein by reference.

Hydrazone transport molecules, such as p-diethylaminobenzaldehyde-(diphenylhydrazone),o-ethoxy-p-diethylaminobenzaldehyde-(diphenylhydrazone),o-methyl-p-diethylaminobenzaldehyde-(diphenylhydrazone),o-methyl-p-dimethylaminobenzaldehyde-(diphenylhydrazone),1-naphthalenecarbaldehyde 1-methyl-1-phenylhydrazone,1-naphthalenecarbaldehyde 1,1-phenylhydrazone,4-methoxynaphthlene-1-carbaldeyde 1-methyl-1-phenylhydrazone, and thelike. Other examples of hydrazone transport molecules are described, forexample in U.S. Pat. Nos. 4,150,987, 4,385,106, 4,338,388, and4,387,147, the disclosures of each of which are totally incorporatedherein by reference.

Carbazole phenyl hydrazone transport molecules such as9-methylcarbazole-3-carbaldehyde-1,1-diphenylhydrazone,9-ethylcarbazole-3-carbaldehyde-1-methyl-1-phenylhydrazone,9-ethylcarbazole-3-carbaldehyde-1-ethyl-1-phenylhydrazone,9-ethylcarbazole-3-carbaldehyde-1-ethyl-1-benzyl-1-phenylhydrazone,9-ethylcarbazole-3-carbaldehyde-1,1-diphenylhydrazone, and the like.Other examples of carbazole phenyl hydrazone transport molecules aredescribed, for example, in U.S. Pat. Nos. 4,256,821 and 4,297,426, thedisclosures of each of which are totally incorporated herein byreference.

Vinyl-aromatic polymers such as polyvinyl anthracene,polyacenaphthylene; formaldehyde condensation products with variousaromatics such as condensates of formaldehyde and 3-bromopyrene;2,4,7-trinitrofluorenone, and 3,6-dinitro-N-t-butylnaphthalimide asdescribed, for example, in U.S. Pat. No. 3,972,717, the disclosure ofwhich is totally incorporated herein by reference.

Oxadiazole derivatives such as2,5-bis-(p-diethylaminophenyl)-oxadiazole-1,3,4 described in U.S. Pat.No. 3,895,944, the disclosure of which is totally incorporated herein byreference.

Tri-substituted methanes such as alkyl-bis(N,N-dialkylaminoaryl)methane,cycloalkyl-bis(N,N-dialkylaminoaryl)methane, andcycloalkenyl-bis(N,N-dialkylaminoaryl)methane as described in U.S. Pat.No. 3,820,989, the disclosure of which is totally incorporated herein byreference. 9-Fluorenylidene methylene derivatives having the formula

wherein X and Y are cyano groups or alkoxycarbonyl groups; A, B, and Ware electron withdrawing groups independently selected from the groupconsisting of acyl, alkoxycarbonyl, nitro, alkylaminocarbonyl, andderivatives thereof; m is a number of from 0 to 2; and n is the number 0or 1 as described in U.S. Pat. No. 4,474,865, the disclosure of which istotally incorporated herein by reference. Examples of 9-fluorenylidenemethylene derivatives encompassed by the above formula include(4-n-butoxycarbonyl-9-fluorenylidene)malonontrile,(4-phenethoxycarbonyl-9-fluorenylidene) malonontrile,(4-carbitoxy-9-fluorenylidene)malonontrile,(4-n-butoxycarbonyl-2,7-dinitro-9-fluorenylidene)malonate, and the like.

Other charge transport materials include poly-1-vinylpyrene,poly-9-vinylanthracene, poly-9-(4-pentenyl)-carbazole,poly-9-(5-hexyl)-carbazole, polymethylene pyrene,poly-1-(pyrenyl)-butadiene, polymers such as alkyl, nitro, amino,halogen, and hydroxy substitute polymers such as poly-3-amino carbazole,1,3-dibromo-poly-N-vinyl carbazole, 3,6-dibromo-poly-N-vinyl carbazole,and numerous other transparent organic polymeric or non-polymerictransport materials as described in U.S. Pat. No. 3,870,516, thedisclosure of which is totally incorporated herein by reference. Alsosuitable as charge transport materials are phthalic anhydride,tetrachlorophthalic anhydride, benzil, mellitic anhydride,S-tricyanobenzene, picryl chloride, 2,4-dinitrochlorobenzene,2,4-dinitrobromobenzene, 4-nitrobiphenyl, 4,4-dinitrophenyl,2,4,6-trinitroanisole, trichlorotrinitrobenzene, trinitro-o-toluene,4,6-dichloro-1,3-dinitrobenzene, 4,6-dibromo-1,3-dinitrobenzene,p-dinitrobenzene, chloranil, bromanil, and mixtures thereof,2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitrofluorenone,trinitroanthracene, dinitroacridene, tetracyanopyrene,dinitroanthraquinone, polymers having aromatic or heterocyclic groupswith more than one strongly electron withdrawing substituent such asnitro, sulfonate, sulfonyl, carboxyl, cyano, or the like, includingpolyesters, polysiloxanes, polyamides, polyurethanes, and epoxies, aswell as block, graft, or random copolymers containing the aromaticmoiety, and the like, as well as mixtures thereof, as described in U.S.Pat. No. 4,081,274, the disclosure of which is totally incorporatedherein by reference.

Also suitable are charge transport materials such as triarylamines,including tritolyl amine, of the formula

and the like, as disclosed in, for example, U.S. Pat. Nos. 3,240,597 and3,180,730, the disclosures of each of which are totally incorporatedherein by reference, and substituted diarylmethane and triarylmethanecompounds, including bis-(4-diethylamino-2-methylphenyl)-phenylmethane,of the formula

and the like, as disclosed in, for example, U.S. Pat. Nos. 4,082,551,3,755,310, 3,647,431, British Patent 984,965, British Patent 980,879,and British Patent 1,141,666, the disclosures of each of which aretotally incorporated herein by reference.

One specific example of a charge transport molecule is one having thegeneral formula

wherein X, Y and Z are each, independently of the others, hydrogen,alkyl groups having from 1 to about 20 carbon atoms, or chlorine, andwherein at least one of X, Y and Z is independently selected to be analkyl group having from 1 to about 20 carbon atoms or chlorine. If Y andZ are hydrogen, the compound can be namedN,N′-diphenyl-N,N′-bis(alkylphenyl)-[1,1′-biphenyl]-4,4′-diamine whereinthe alkyl is, for example, methyl, ethyl, propyl, n-butyl, or the like,or the compound can beN,N′-diphenyl-N,N′-bis(chlorophenyl)-[1,1′-biphenyl]-4,4′-diamine. Aspecific member of this class isN,N′-diphenyl-N,N′-bis(3″-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine(prepared as disclosed in U.S. Pat. No. 4,265,990, the disclosure ofwhich is totally incorporated herein by reference).

Any suitable and conventional technique can be utilized to mix andthereafter apply the charge transport layer coating mixture to thecharge generating layer. Examples of application techniques includespraying, dip coating, roll coating, wire wound rod coating, and thelike. Drying of the deposited coating can be effected by any suitableconventional technique such as oven drying, infra red radiation drying,air drying, and the like.

The charge transport material is present in the charge transport layerin any effective amount, in one embodiment from about 5 to about 90percent by weight, in another embodiment from about 20 to about 75percent by weight, in yet another embodiment from about 20 to about 60percent by weight, and in still another embodiment from about 30 toabout 60 percent by weight, although the amount can be outside of theseranges.

Examples of the highly insulating and transparent resinous components orinactive binder resinous material for the transport layers includematerials such as those described in U.S. Pat. No. 3,121,006, thedisclosure of which is totally incorporated herein by reference.Specific examples of suitable organic resinous materials includepolycarbonates, acrylate polymers, vinyl polymers, cellulose polymers,polyesters, polysiloxanes, polyamides, polyurethanes, polystyrenes,polyarylates, polyethers, polysulfones, and epoxies, as well as block,random or alternating copolymers thereof. Examples of electricallyinactive binder materials include polycarbonate resins having a numberaverage molecular weight of from about 20,000 to about 100,000 with amolecular weight in the range of from about 50,000 to about 100,000being one specific embodiment. The branched polymers as disclosed hereincan also be employed as the binder in the charge transport layer of theimaging member, either alone or in combination with other materials. Thecharge transport layer contains the charge transport material in anamount in one embodiment of from about 5 to about 90 percent by weight,and in another embodiment from about 20 percent to about 75 percent byweight, although the relative amounts of binder and transport materialcan be outside these ranges.

Generally, the thickness of the charge transport layer is from about 10to about 50 microns, although thicknesses outside of this range can alsobe used. In one specific embodiment, the ratio of the thickness of thecharge transport layer to the charge generator layer is maintained fromabout 2:1 to 200:1, and in some instances as great as 400:1.

At least one layer of the imaging members disclosed herein, such as theadhesive layer, the protective overcoat layer, the photogeneratinglayer, the charge transport layer, or the like, contains a branchedpolymer as disclosed herein. The branched polymer can be present as thesole binder in the layer, or can be present as a component of a blend oftwo or more binder polymers. One example of a suitable polymer withwhich the branched polymers as disclosed herein can be blended is apolycarbonate resin. Any desired or suitable polycarbonate resin can beselected. For example, polycarbonates of the general formula

wherein R and R′ each, independently of the other, is an alkyl group(including cycloalkyl groups and substituted alkyl groups), in oneembodiment with from 1 to about 30 carbon atoms, or a phenyl group(including substituted phenyl groups) and n is an integer representingthe number of repeat monomer units, in one embodiment being from about10 to about 1,000, although the value can be outside of this range.Examples of polycarbonates include poly(4,4′-isopropylidene-diphenylene)carbonate (also referred to as bisphenol-A-polycarbonate),poly(4,4′-diphenyl-1,1′-cyclohexane) carbonate, and the like. Somepolycarbonate resins have a number average molecular weight of fromabout 20,000 to about 150,000, with a number average molecular weight inthe range of from about 50,000 to about 100,000 being another specificembodiment. Some polycarbonate resins have a weight average molecularweight of from about 20,000 to about 100,000, with a weight averagemolecular weight in the range of from about 50,000 to about 100,000being another specific embodiment. Within the layer, the additionalbinder components, such as a polycarbonate, and the branched polymer asdisclosed herein can be blended in any suitable or desired relativeamounts, in one embodiment from about 1 to about 99 percent by weight ofthe second binder polymer and from about 1 to about 99 percent by weightof the branched polymer as disclosed herein, in another embodiment fromabout 5 to about 95 percent by weight of the second binder polymer andfrom about 5 to about 95 percent by weight of the branched polymer asdisclosed herein, and in yet another embodiment from about 25 to about75 percent by weight of the second binder polymer and from about 25 toabout 75 percent by weight of the branched polymer as disclosed herein,although the relative amounts can be outside these ranges.

Other layers, such as conventional electrically conductive ground stripalong one edge of the belt in contact with the conductive layer,blocking layer, adhesive layer or charge generating layer to facilitateconnection of the electrically conductive layer of the photoreceptor toground or to an electrical bias, can also be included. Ground strips arewell known and usually comprise conductive particles dispersed in a filmforming binder.

Optionally, an overcoat layer can also be utilized to improve resistanceto abrasion. In some cases an anti-curl back coating can be applied tothe surface of the substrate opposite to that bearing thephotoconductive layer to provide flatness and/or abrasion resistance.These overcoating and anti-curl back coating layers are well known inthe art and can comprise thermoplastic organic polymers or inorganicpolymers that are electrically insulating or slightly semi-conductive.Overcoatings are continuous and generally have a thickness of less thanabout 10 micrometers. The thickness of anti-curl backing layers shouldbe sufficient to substantially balance the total forces of the layer orlayers on the opposite side of the supporting substrate layer. The totalforces are substantially balanced when the belt has no noticeabletendency to curl after all the layers are dried. For example, for anelectrophotographic imaging member in which the bulk of the coatingthickness on the photoreceptor side of the imaging member is a transportlayer containing predominantly polycarbonate resin and having athickness of about 24 microns on a Mylar substrate having a thickness ofabout 76 microns, sufficient balance of forces can be achieved with a13.5 micrometers thick anti-curl layer containing about 99 percent byweight polycarbonate resin, about 1 percent by weight polyester andbetween about 5 and about 20 percent of coupling agent treatedcrystalline particles. An example of an anti-curl backing layer isdescribed in U.S. Pat. No. 4,654,284 the disclosure of which is totallyincorporated herein by reference. A thickness between about 70 and about160 microns is a satisfactory range for flexible photoreceptors.Branched polymers as disclosed herein are also suitable for use asovercoat layers and anticurl back coating layers.

Also disclosed herein is a method of generating images with thephotoconductive imaging members disclosed herein. The method comprisesthe steps of generating an electrostatic latent image on aphotoconductive imaging member as disclosed herein, developing thelatent image, and transferring the developed electrostatic image to asubstrate. Optionally, the transferred image can be permanently affixedto the substrate. Development of the image can be achieved by a numberof methods, such as cascade, touchdown, powder cloud, magnetic brush,and the like. Transfer of the developed image to a substrate can be byany method, including those making use of a corotron or a biasedcharging roll. The fixing step can be performed by means of any suitablemethod, such as radiant flash fusing, heat fusing, pressure fusing,vapor fusing, and the like. Any material used in xerographic copiers andprinters can be used as a substrate, such as paper, transparencymaterial, or the like.

Specific embodiments will now be described in detail. These examples areintended to be illustrative, and the claims are not limited to thematerials, conditions, or process parameters set forth in theseembodiments. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE I

To a 1 liter resin jar fitted with a turbine mechanical stirring shaft,argon inlet, and Dean-Stark trap (topped with a water cooled condenser)was added sequentially 150 grams of polysulfone (PAES,poly-bisphenol-A-co-4,4-dichlorodiphenylsulfone, obtained from AldrichChemical Company, Mississauga, Ontario, Canada, Mn 26,000 (advertised))and 450 grams of N,N-dimethylacetamide (DMAc, A.C.S. reagent grade,obtained from Aldrich Chemical Company, Mississauga, Ontario, Canada).The mixture was heated slightly (50° C.) and stirred (350 rpm) todissolve the polymer completely. To this solution was then added 150milliliters of toluene (A.C.S. reagent grade, obtained from AldrichChemical Company, Mississauga, Ontario, Canada), 10.5 grams of1,1,1-tris(4-hydroxyphenyl)ethane (THPE, obtained from Aldrich ChemicalCompany, Mississauga, Ontario, Canada), and 10.5 grams of cesiumcarbonate (obtained from Aldrich Chemical Company, Mississauga, Ontario,Canada). The mixture was heated at reflux for 19 hours. The solution wasthen cooled to room temperature, filtered through a pad of CELITE®), andprecipitated into 8 liters of vigorously stirred methanol (obtained fromCaledon Laboratories, Georgetown, Ontario, Canada). The resultingprecipitate was isolated by vacuum filtration through #1 Whatman filterpaper, followed by stirring in 5 liters of deionized water for 1 hour,refiltration, subsequent stirring in 5 liters of methanol for 1 hour,and a final filtration. The precipitate was dried in a vacuum oven (30°C., 7 mmHg) for three days to yield a white free flowing powder (yield90 percent). Incorporation of the tris(4-hydroxyphenyl)ethane moietywere confirmed by ¹H NMR [δ CH₃(THPE)=1.64 (TMS)].

EXAMPLE II

The process of Example I was repeated except that 15.75 grams of1,1,1-tris(4-hydroxyphenyl)ethane was used instead of 10.5 grams of1,1,1-tris(4-hydroxyphenyl)ethane.

EXAMPLE III

The process of Example I was repeated except that 21.0 grams of1,1,1-tris(4-hydroxyphenyl)ethane was used instead of 10.5 grams of1,1,1-tris(4-hydroxyphenyl)ethane.

Measured values (by gas phase chromatography) for number averagemolecular weight, weight average molecular weight, and polydispersityvalues for the starting polysulfone material and the products ofExamples I, II, and III are as follows:

Polydispersity M_(n) M_(w) M_(p) (M_(w)/M_(n)) PAES 43,201 70,109 70,7451.62 Ex. I 10,310 26,277 24,970 2.54 Ex. II 8,853 22,086 23,363 2.49 Ex.III 7,289 16,599 19,302 2.21Because gas phase chromatography measures hydrodynamic volume bymeasuring retention time, it is believed that the values above indicatevarying degrees of branching within the polymers thus formed, sincebranching in polymers leads to decreased hydrodynamic volume andincreased GPC retention time.

EXAMPLE IV

To a 1 liter resin jar fitted with a turbine mechanical stirring shaft,argon inlet, and Dean-Stark trap (topped with a water cooled condenser)was added sequentially 83.99 grams of1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol-Z, obtained from AldrichChemical Company, Mississauga, Ontario, Canada), 68.32 g4,4′-difluorobenzophenone (obtained from Oakwood Chemicals, WestColumbia, S.C., USA and Honeywell Specialty Chemicals, Morristown, N.J.,USA), 61 grams of potassium carbonate (A.C.S. reagent grade, obtainedfrom Caledon Laboratories, Georgetown, Ontario, Canada), 400 grams ofN,N-dimethylacetamide (DMAc, A.C.S. reagent grade, obtained from AldrichChemical Company, Mississauga, Ontario, Canada), and 150 grams oftoluene (A.C.S. reagent grade, obtained from Aldrich Chemical Company(Mississauga, Ontario, Canada). The mixture was heated at reflux for 19hours. The solution was then cooled to room temperature, diluted with400 grams of DMAC, filtered through a pad of CELITE®, and precipitatedinto 8 liters of vigorously stirred methanol (obtained from CaledonLaboratories, Georgetown, Ontario, Canada). The resulting precipitatewas isolated by vacuum filtration through #1 Whatman filter paper,followed by stirring in 5 liters of deionized water for 1 hour,refiltration, subsequent stirring in 5 liters of methanol for 1 hour,and a final filtration. The precipitate was dried in a vacuum oven (30°C., 7 mmHg) for three days to yield a white free flowing powder (yield 6percent). The polymer was measured to have Mw 46,300 Daltons and Mn29,300 Daltons by GPC relative to polystyrene standards.

EXAMPLE V

To a 500 liter resin jar fitted with a turbine mechanical stirringshaft, argon inlet, and Dean-Stark trap (topped with a water cooledcondenser) was added sequentially 65 grams of the polymer prepared inExample IV (poly-bisphenol-Z-co-4,4-didifluorobenzophenone) and 225grams of N,N-dimethylacetamide (DMAc, A.C.S. reagent grade, obtainedfrom Aldrich Chemical Company, Mississauga, Ontario, Canada). Themixture was heated slightly (50° C.) and stirred (350 rpm) to dissolvethe polymer completely. To this mixture was added 50 milliliters oftoluene (A.C.S. reagent grade, obtained from Aldrich Chemical Company,Mississauga, Ontario, Canada), 7.85 grams of1,1,1-tris(4-hydroxyphenyl)ethane (THPE, obtained from Aldrich ChemicalCompany, Mississauga, Ontario, Canada), and 25.0 grams of cesiumcarbonate (obtained from Aldrich Chemical Company, Mississauga, Ontario,Canada). The mixture was heated at reflux for 19 hours. The solution wasthen cooled to room temperature, filtered through a pad of CELITE®, andprecipitated into 4 liters of vigorously stirred methanol (obtained fromCaledon Laboratories, Georgetown, Ontario, Canada). The resultingprecipitate was isolated by vacuum filtration through #1 Whatman filterpaper, followed by stirring in 2.5 liters of deionized water for 1 hour,refiltration, subsequent stirring in 2.5 liters of methanol for 1 hour,and a final filtration. The precipitate was dried in a vacuum oven (30°C., 7 mmHg) for three days to yield a white free flowing powder (yield90 percent). Incorporation of the tris(4-hydroxyphenyl)ethane moietywere confirmed by ¹H NMR [δ CH₃(THPE)=1.64(TMS)].

EXAMPLE VI

The polymers prepared in Examples I, III, and V (2.00 grams in eachinstance) are each roll milled in an amber glass bottle with methylenechloride (22.44 grams in each instance) andN,N′-diphenyl-N,N′-bis(3″-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine(2.00 grams in each instance) (charge transport material, prepared asdisclosed in U.S. Pat. No. 4,265,990, the disclosure of which is totallyincorporated herein by reference). The resulting solutions are eachcoated onto the photogenerating layers of imaging members comprising a 3mil thick polyethylene terephthalate substrate, a vacuum depositedtitanium oxide coating about 200 Angstroms thick, a3-aminopropyltriethoxysilane charge blocking layer 300 Angstroms thick,a 49 micron thick polyester adhesive layer (49,000, available from E.I.du Pont de Nemours & Co., Wilmington, Del.) about 400 Angstroms thick,and a 2.5 micron thick photogenerating layer containing 7.5 percent byvolume trigonal selenium, 25 percent by volumeN,N′-diphenyl-N,N′-bis(3″-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine,and a polyvinylcarbazole binder (67.5 percent by volume) (available fromBASF, Mt. Olive, N.J.). The photogenerating layer in each instance isprepared by introducing 8 grams of polyvinyl carbazole and 140milliliters of a 1:1 volume ratio of a mixture of tetrahydrofuran andtoluene into a 20 ounce amber bottle. To this solution is added 8 gramsof trigonal selenium and 1,000 grams of ⅛ inch (3.2 milliliter) diameterstainless steel shot. This mixture is then placed on a ball mill for 96hours. Subsequently, 50 grams of the resulting slurry are added to asolution of 3.6 grams of polyvinyl carbazole and 20 grams ofN,N′-diphenyl-N,N′-bis(3″-methylphenyl)-(1,1′-biphenyl)-4,4′-diaminedissolved in 75 milliliters of 1:1 volume ratio oftetrahydrofuran/toluene. This slurry is then placed on a shaker for 10minutes. The resulting slurry is thereafter applied to the adhesiveinterface by extrusion coating to form a layer having a wet thickness of0.5 mil (12.7 microns). This photogenerating layer is dried at 135° C.for 5 minutes in a forced air oven to form a dry thickness of 2.0microns. (This process for preparing a photogenerating layer is alsodisclosed in U.S. Pat. No. 5,308,725, the disclosure of which is totallyincorporated herein by reference).

Charge transport layers are then applied to the photogenerating layersthus prepared. Charge transport solutions are prepared in each instanceby introducing into an amber glass bottle 2.00 grams ofN,N′-diphenyl-N,N′-bis(3″-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine,2.00 grams of the same polymer used as the binder in the photogeneratinglayer, and 22.44 grams of methylene chloride and admixing the contentsto prepare the solution. The charge transport solutions are applied tothe photogenerator layers with a 8 mil gap Bird applicator to form acoating which is heated from 40 to 100° C. over 30 minutes to dry thelayer. The charge transport layers thus applied to the imaging membershave dry coating thicknesses of about 25 microns.

Other embodiments and modifications may occur to those of ordinary skillin the art subsequent to a review of the information presented herein;these embodiments and modifications, as well as equivalents thereof, arealso included within the scope of this invention.

The recited order of processing elements or sequences, or the use ofnumbers, letters, or other designations therefor, is not intended tolimit a claimed process to any order except as specified in the claimitself.

1. A process for preparing a branched polyarylene ether polymer whichcomprises (A) providing a reaction mixture which comprises (i) anoptional solvent, (ii) a polyfunctional phenol compound of the formulaAr(OH)_(x) wherein x≧3 and wherein Ar is an aryl moiety or an alkylarylmoiety, provided that when Ar is an alkylaryl moiety at least three ofthe —OH groups are bonded to an aryl portion thereof, (iii) one or morelinear polymers of the formula

wherein each m, independently of the others, is an integer of 0 or 1,each A, independently of the others, is

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R_(x) is an alkylene group, an arylene group, an arylalkylenegroup, an alkylarylene group, or mixtures thereof,

or mixtures thereof, each B, independently of the others, is

wherein z is an integer of from 2 to about 20,

wherein u is an integer of from 1 to about 20,

wherein w is an integer of from 1 to about 20,

wherein each o, independently of the other, is an integer of 1, 2, 3, or4,

wherein R₁ and R₂ each, independently of the other, are hydrogen atoms,alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, ormixtures thereof, and p is an integer of 0 or 1,

wherein b is an integer of 0 or 1,

wherein (1) Z is

wherein c is 0 or 1; (2) Ar′ is

(3) G is an alkyl group selected from alkyl groups containing from about2 to about 10 carbon atoms; (4) Ar″ is

wherein s is 0, 1, or 2,

and (6) q is 0 or 1; or mixtures thereof, and n is an integerrepresenting the number of repeat monomer units, (iv) optionally, acompound of the formula

wherein a is an integer of from 1 to 5 and R′ is a hydrogen atom, analkyl group, an aryl group, an arylalkyl group, an alkylaryl group, or amixture thereof, wherein two or more R′ groups can be joined together toform a ring, and (v) a carbonate base; and (B) heating the reactionmixture and removing generated water from the reaction mixture, therebyeffecting a polymerization reaction.
 2. A process according to claim 1wherein A is

or a mixture thereof and B is

wherein z is an integer of from 2 to about 20,

or a mixture thereof.
 3. A process according to claim 1 wherein A is


4. A process according to claim 1 wherein A is


5. A process according to claim 1 wherein A is


6. A process according to claim 1 wherein A is


7. A process according to claim 1 wherein Ar is a substituted aryl groupor a substituted arylalkyl group.
 8. A process according to claim 1wherein Ar is an unsubstituted aryl group or an unsubstituted arylalkylgroup.
 9. A process according to claim 1 wherein Ar is an aryl grouphaving one or more hetero atoms therein or an arylalkyl group having oneor more hetero atoms therein.
 10. A process according to claim 9 whereinthe one or more hetero atoms is oxygen, nitrogen, sulfur, silicon,phosphorus, or a mixture thereof.
 11. A process according to claim 1wherein Ar is an aryl group having no hetero atoms therein or anarylalkyl group having no hetero atoms therein.
 12. A process accordingto claim 1 wherein x is
 3. 13. A process according to claim 1 whereinthe polyfunctional phenol is


14. A process according to claim 1 wherein the polyfunctional phenol is(a) of the formula

wherein y is an integer of 1, 2, or 3, z is an integer representing thenumber of HO-φ-CH_(3−y)— groups on R_(d), and R_(d) is a monovalentmoiety; (b) of the formula

wherein r is an integer of at least about 3 and R_(e) is an alkyl group,an aryl group, an arylalkyl group, or an alkylaryl group, (c) of theformula

wherein f is an integer of at least 3, (d) of the formula

wherein g₁, g₂, g₃, and g₄ are each integers of 0, 1, 2, 3, or 4,provided that the sum of g₁+g₂+g₃+g₄≧3, (e) of the formula

wherein h₁, h₂, h₃, and h₄ are each integers of 0, 1, 2, 3, or 4,provided that the sum of h₁+h₂+h₃+h₄≧3, (f) of the formula

wherein j₁, j₂, j₃, and j₄ are each integers of 0, 1, 2, 3, or 4,provided that the sum of j₁+j₂+j₃+j₄≧3, or (g) mixtures thereof.
 15. Aprocess according to claim 1 wherein the polyfunctional phenol is1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,3,3,3′,3′-tetramethyl-1,1′-spirobisindane-5,5′,6,6′-tetrol, pyrogallol,1,2,4-benzenetriol, phloroglucinol dihydrate, dithranol,nordihydroguaiaretic acid, C-methylcalix(4)resorcinarene,C-undecylcalix(4)-resorcinarene monohydrate, catechin hydrate,epicatechin, or mixtures thereof.
 16. A process according to claim 1wherein a solvent is present.
 17. A process according to claim 16wherein the solvent is N,N-dimethylacetamide, sulfolane, dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidinone,hexamethylphosphoric triamide, or mixtures thereof.
 18. A processaccording to claim 1 wherein the compound of the formula

is present.
 19. A process according to claim 18 wherein


20. A process according to claim 18 wherein

is a methyl phenol, an ethyl phenol, a propyl phenol, a butyl phenol, apentyl phenol, a hexyl phenol, a heptyl phenol, an octyl phenol, a nonylphenol, a decyl phenol, an undecyl phenol, a dodecyl phenol, a phenylphenol, a tolyl phenol, a benzyl phenol, a methoxy phenol, an ethoxyphenol, a propoxy phenol, a butoxy phenol, a pentyloxy phenol, ahexyloxy phenol, a heptyloxy phenol, an octyloxy phenol, a nonyloxyphenol, a decyloxy phenol, an undecyloxy phenol, a dodecyloxy phenol, aphenoxy phenol, a tolyloxy phenol, a benzyloxy phenol, a(polyethyleneoxy) phenol, a (polypropyleneoxy) phenol, a(polybutyleneoxy) phenol, a naphthol, or a mixture thereof.
 21. Aprocess according to claim 1 wherein the carbonate base is lithiumcarbonate, sodium carbonate, potassium carbonate, cesium carbonate, or amixture thereof.
 22. A process according to claim 1 wherein thecarbonate base is potassium carbonate.
 23. A process according to claim1 wherein the carbonate base is cesium carbonate.
 24. A processaccording to claim 1 wherein a solvent is present and wherein thereaction mixture is heated to reflux temperature.
 25. A processaccording to claim 1 wherein water is removed from the reaction mixtureby azeotropic distillation.
 26. A process according to claim 25 whereinthe azeotropic distillation is carried out with toluene.
 27. A processaccording to claim 1 wherein the linear polymer is

or mixtures thereof.
 28. A process according to claim 1 wherein thereaction mixture further contains a dihalogenated compound of theformula

or mixtures thereof, wherein Y and Y′ each, independently of the other,is a fluorine atom or a chlorine atom.
 29. A process according to claim28 wherein the dihalogenated compound is

or mixtures thereof.
 30. A process according to claim 28 wherein thecompound of the formula

is present, wherein the dihalogenated compound is present in an amountof at least about 0.4 mole of dihalogenated compound per every one moleof compound of the formula

and wherein the dihalogenated compound is present in an amount of nomore than about 0.6 mole of dihalogenated compound per every one mole ofcompound of the formula


31. A process according to claim 28 wherein x is 3, wherein thedihalogenated compound is present in an amount of at least about 1.4moles of dihalogenated monomer per every one mole of polyfunctionalphenol compound, and wherein the dihalogenated compound is present in anamount of no more than about 1.6 moles of dihalogenated monomer perevery one mole of polyfunctional phenol compound.
 32. A process forpreparing a branched polyarylene ether polymer which comprises (A)providing a reaction mixture which comprises (i) a solvent, (ii) apolyfunctional phenol compound of the formula Ar(OH)_(x) wherein x≧3 andwherein Ar is an aryl moiety or an alkylaryl moiety, provided that whenAr is an alkylaryl moiety at least three of the —OH groups are bonded toan aryl portion thereof, (iii) one or more linear polymers of theformula

wherein each m, independently of the others, is an integer of 0 or 1,each A, independently of the others, is

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R_(x) is an alkylene group, an arylene group, an arylalkylenegroup, an alkylarylene group, or mixtures thereof,

or mixtures thereof, each B, independently of the others, is

wherein z is an integer of from 2 to about 20,

wherein u is an integer of from 1 to about 20,

wherein w is an integer of from 1 to about 20,

wherein each o, independently of the other, is an integer of 1, 2, 3, or4,

wherein R₁ and R₂ each, independently of the other, are hydrogen atoms,alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, ormixtures thereof, and p is an integer of 0 or 1,

wherein b is an integer of 0 or 1,

wherein (1) Z is

wherein c is 0 or 1; (2) Ar′ is

(3) G is an alkyl group selected from alkyl groups containing from about2 to about 10 carbon atoms; (4) Ar″ is

wherein s is 0, 1, or 2,

and (6) q is 0 or 1; or mixtures thereof, and n is an integerrepresenting the number of repeat monomer units, (iv) a compound of theformula

wherein a is an integer of from 1 to 5 and R′ is a hydrogen atom, analkyl group, an aryl group, an arylalkyl group, an alkylaryl group, or amixture thereof, wherein two or more R′ groups can be joined together toform a ring, (v) a carbonate base, and (vi) a dihalogenated monomercompound of the formula

or mixtures thereof, wherein Y and Y′ each, independently of the other,is a fluorine atom or a chlorine atom; and (B) heating the reactionmixture and removing generated water from the reaction mixture, therebyeffecting a polymerization reaction.
 33. A process for preparing abranched polyarylene ether polymer which comprises (A) providing areaction mixture which comprises (i) a solvent, (ii) a polyfunctionalphenol compound of the formula Ar(OH)_(x) wherein x≧3 and wherein Ar isan aryl moiety or an alkylaryl moiety, provided that when Ar is analkylaryl moiety at least three of the —OH groups are bonded to an arylportion thereof, (iii) one or more linear polymers of the formula

wherein each m, independently of the others, is an integer of 0 or 1,each A, independently of the others, is

wherein R is a hydrogen atom, an alkyl group, an aryl group, anarylalkyl group, an alkylaryl group, or mixtures thereof,

wherein R_(x) is an alkylene group, on arylene group, an arylalkylenegroup, an alkylarylene group, or mixtures thereof,

or mixtures thereof, each B, independently of the others, is

wherein z is an integer of from 2 to about 20,

wherein u is an integer of from 1 to about 20,

wherein w is an integer of from 1 to about 20,

wherein each o, independently of the other, is an integer of 1, 2, 3, or4,

wherein R₁ and R₂ each, independently of the other, are hydrogen atoms,alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, ormixtures thereof, and p is an integer of 0 or 1,

wherein b is an integer of 0 or 1,

wherein (1)Z is

wherein c is 0 or 1; (2) Ar′ is

(3) G is an alkyl group selected from alkyl groups containing from about2 to about 10 carbon atoms; (4) Ar″ is

wherein s is 0, 1, or 2,

and (6) q is 0 or 1; or mixtures thereof, and n is an integerrepresenting the number of repeat monomer units, (iv) a carbonate base,and (v) a dihalogenated monomer compound of the formula

or mixtures thereof, wherein Y and Y′ each, independently of the other,is a fluorine atom or a chlorine atom; and (B) healing the reactionmixture and removing generated water from the reaction mixture, therebyeffecting a polymerization reaction.